Crystal form of compound containing five-membered heterocyclic ring, and preparation method therefor

Abstract

The present invention specifically relates to a crystal form of a compound containing a five-membered heterocyclic ring, and a preparation method therefor. The crystal form of a compound containing a five-membered heterocyclic ring has excellent heat storage stability, and a suspension concentrate prepared from the crystal form is easy to store, and has a low drainage rate, high suspensibility and good formulation flowability. In addition, the crystal form achieves a nanoscale product particle size, better adhesion to leaves and pest mites under small-scale effects, high pesticide retention, faster permeation and absorption due to a small particle size, faster pesticide effects, and high rainfastness.

Description

Crystalline form of compound containing five-membered heterocycle and preparation method thereof

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202410451283.5, filed on April 16, 2024, the contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present application belongs to the field of compound crystalline forms, and specifically relates to a crystalline form of a compound containing a five-membered heterocycle and a preparation method thereof. BACKGROUND

[0004] Pests and mites harm hundreds of plants, especially vegetables, flowers and fruit trees, causing serious economic losses. Aryl isoxazoline derivatives containing heterocyclic compounds have unique insecticidal activity in modern crop and animal protection, such as the first isoxazoline insecticide flupyradifuram developed by Nissan Chemical.

[0005] Although the compound has outstanding performance in insecticidal and miticidal aspects, it still faces some challenges in practical application due to some physicochemical property characteristics. Therefore, how to simply and effectively improve its physicochemical properties is a key factor for further development and application of the compound. The commonly used methods for changing its properties usually need to change its structure or add additives, which not only has high cost, but also has uncertain effect. Therefore, there is an urgent need for a method for improving the physicochemical properties, biological activity, etc. of the compound and its preparation. SUMMARY

[0006] The purpose of the present application is to further improve the physicochemical properties of the compound as shown in formula A, improve the bioavailability, solubility, chemical and physical stability, density or flowability, etc. of the compound, and make it better play the insecticidal and miticidal activity, and facilitate the preparation in the production process of pesticide preparation.

[0007] In order to achieve the above technical purpose, the present application provides the following technical scheme: a crystalline form I of a compound containing a five-membered heterocycle, the compound containing a five-membered heterocycle has a structure as shown in formula A:

[0008] Form I exhibits at least three of the following diffraction peaks, given in degrees of two-theta, in an X-ray powder diffraction pattern: 5.32, 5.66, 11.92, 13.96, 14.1, 15.94, 16.96, 17.16, 18.54, 18.84, 19.08, 19.3, 19.38, 19.40, 19.44, 19.52, 20.14, 20.24, 21.42, 21.52, 22.74, 25.76, 27.58, 33.14, 34.48, wherein the error range in 2-theta is within ±0.2°.

[0009] Form I exhibits at least three of the following diffraction peaks, given in degrees of two-theta, in an X-ray powder diffraction pattern: 14.20, 17.28, 19.38, 19.40, 19.44, 20.24, 21.42, wherein the error range in 2-theta is within ±0.2°.

[0010] Form I exhibits the following diffraction peaks, given in degrees of two-theta, in an X-ray powder diffraction pattern: 5.32, 5.46, 5.66, 7.54, 8.86, 9.06, 11.92, 12.92, 13.64, 13.96, 14.1, 14.2, 14.92, 15.18, 15.94, 16.96, 17.16, 17.28, 17.94, 18.54, 18.84, 19.08, 19.3, 19.38, 19.40, 19.44, 19.52, 20.1, 20.14, 20.24, 20.72, 21.1, 21.42, 21.52, 21.92, 22.74, 23.66, 24.14, 24.88, 25.56, 25.76, 26.5, 27.58, 28.44, 28.68, 29.46, 30.72, 31.66, 33.14, 34.48, 35.38, 35.96, 36.26, 38.8, 39, 40.2, 40.68, wherein the error range in 2-theta is within ±0.2°.

[0011] Form I has an X-ray powder diffraction pattern as shown in FIG. 1.

[0012] A crystalline Form II of a five-membered heterocycle-containing compound having the structure of Formula A:

[0013] Form II exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 5.02, 11.88, 14.98, 15.02, 19.14, 19.16, 19.22, 19.24, 19.28, 19.36, 19.38, 19.40, 19.42, 19.46, 19.48, 19.5, 19.52, 19.54, 19.56, 19.58, 22.62, 27.00, 27.04, 27.06, 27.08, 27.10, wherein the error range in 2-theta is within ±0.2°.

[0014] Form II exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 15.02, 19.42, 19.46, 19.48, 19.52, 22.62, 27.06, 27.10, wherein the error range in 2-theta is within ±0.2°.

[0015] Form II exhibits the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 5.02, 5.1, 6.12, 7.16, 8.58, 10.26, 11.72, 11.88, 12.94, 13.96, 14.42, 14.98, 15.02, 19.14, 19.16, 19.22, 19.24, 19.26, 19.28, 19.3, 19.34, 19.36, 19.38, 19.4, 19.42, 19.46, 19.48, 19.5, 19.52, 19.54, 19.56, 19.58, 19.6, 22.58, 22.62, 22.66, 22.68, 24.04, 26.92, 26.94, 26.96, 26.98, 27, 27.04, 27.06, 27.08, 27.1, 27.12, 27.72, 27.74, wherein the error range in 2-theta is within ±0.2°.

[0016] Form II has an X-ray powder diffraction pattern as shown in FIG. 2.

[0017] A crystalline Form III of a five-membered heterocycle-containing compound having the structure of Formula A:

[0018] Form III exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 5.80, 6.72, 10.66, 11.94, 13.68, 16.28, 17.56, 19.18, 19.36, 19.44, 19.48, 19.50, 20.68, 21.24, 21.36, 21.42, 22.54, 23.66, 25.00, 27.00, 27.70, 29.46, 31.56, wherein the error in 2-theta is within ±0.2°.

[0019] Form III exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 17.56, 19.18, 19.36, 19.44, 19.48, 19.50, 21.36, 21.42, 22.54, 25.00, 27.70, wherein the error in 2-theta is within ±0.2°.

[0020] Form III exhibits the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 5.1, 5.8, 6.72, 10.66, 11.94, 12.76, 13.68, 14.98, 16.28, 17.56, 18.96, 19.18, 19.36, 19.44, 19.48, 19.50, 19.96, 20.68, 20.88, 21.24, 21.36, 21.42, 21.84, 22.40, 22.54, 22.70, 23.28, 23.66, 24.06, 24.90, 25.00, 25.82, 26.16, 26.70, 27.00, 27.70, 28.14, 28.74, 29.22, 29.46, 30.16, 31.56, 31.96, 32.68, 34.96, 36.4, wherein the error in 2-theta is within ±0.2°.

[0021] Form III has an X-ray powder diffraction pattern as shown in FIG. 3. Form IV of a compound containing a five-membered heterocycle, the compound having a structure as shown in Formula A:

[0022] Form IV exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 5.68, 7.28, 11.90, 15.04, 17.40, 17.54, 19.12, 19.26, 19.34, 19.40, 19.42, 19.50, 21.32, 21.40, 22.66, 26.92, 27.66, 31.54, wherein the error in 2-theta is within ±0.2°.

[0023] Form IV exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 11.90, 17.54, 19.26, 19.34, 19.40, 19.42, 19.50, 26.92, 27.66, wherein the error range for 2-theta is within +0.2°.

[0024] Form IV exhibits the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 5.12, 5.68, 6.98, 7.28, 11.90, 13.72, 14.92, 15.04, 16.92, 17.4, 17.54, 18.6, 19.12, 19.26, 19.34, 19.4, 19.42, 19.5, 19.62, 20.42, 20.96, 21.32, 21.4, 22.4, 22.64, 22.66, 22.8, 23.34, 23.62, 24.1, 24.96, 25.1, 25.98, 26.92, 26.44, 26.92, 27.1, 27.66, 27.68, 28.4, 28.7, 29.32, 29.36, 29.74, 30.26, 31.54, 32.38, 33.1, 34.1, 35.08, wherein the error range for 2-theta is within +0.2°.

[0025] Form IV has an X-ray powder diffraction pattern as shown in Figure 4.

[0026] In a second aspect, the present application provides a preparation method of the crystal form of compound A, comprising the following steps:

[0027] 1) dissolving compound A in a solvent, filtering after heating and stirring;

[0028] 2) standing the filtrate for a period of time to volatilize the solvent, and drying the precipitated solid by suction filtration and washing, to obtain the crystal form of compound A.

[0029] Further, the solvent in step 1) is at least one selected from petroleum ether, methanol, ethanol, isopropanol, n-propanol, tert-butanol, ethylene glycol, 1,2-propanediol, dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, ethyl acetate, toluene, xylene, acetonitrile, tetrahydrofuran, dioxane, methyl tert-butyl ether, acetone, methyl isobutyl ketone, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or water.

[0030] Further, the heating temperature in step 1) is selected from 30-50°C.

[0031] Further, the standing time in step 2) is 3-7 days.

[0032] In a third aspect, the present application provides an insecticidal and miticidal composition comprising the compound A in a crystal form, wherein the crystal form is selected from the group consisting of crystal form I, crystal form II, crystal form III and crystal form IV, and the content of the crystal form is 1% to 50% by weight.

[0033] Further, the insecticidal and miticidal composition further comprises component B, wherein the content of component B is 1% to 50% by weight; and the insecticidal and miticidal composition further comprises an agriculturally or forestry acceptable adjuvant or carrier.

[0034] Further, component B is selected from the following substances: isoprocarb, butansulfuron, bensulfuron, carbofuran, methomyl, fenbutamide, sulfamethoxazole, fenthiocarb, fenoxycarb, bensulfuron, fenoxycarb, fenoxycarb, carbaryl, furamicarb, pirimicarb, cotton boll carb, aldicarb, butanone carb, butanone sulfone carb, oxamyl, thiodicarb, long-lasting carb, ethiofencarb, methiocarb, mixed carb, methomyl, methomyl, phosphamidon, demacarb, dichlorvos, isothiocarb, pyrimidine carb, pyrazocarb, aldicarb, pentocyanamide, thiazocarb, chlorpyrifos, methomyl, combined carb, animal carb, mixed carb, pyrimidine carb ... Phosphorus, profenofos, prothiophos, thioprophos, methidathion, fenitrothion, malathion, phosalone, diazinon, fenthion, pyraclofos, pyridazinon, phosmet, quinalphos, acephate, isofenphos, oxazophos, pyraclofos, butylpyrimidinphos, rice fengsan, terbufos, aphidron, aphidron, dimethoate, omethoate, chlorpyrifos, phosphamidon, dibromophos, quick-killing Phosphorus, trichlorfon, dichlorvos, chlorpyrifos, cadusin, dicrotophos, methyl chlorpyrifos, propanofos, sulfoxide, heptylphos, naphthiophos, housefly phosphorus, coumaphos, ethiophos, methyl ethiophos, ethiophos, ethoprophos, chlorpyrifos, azophos, azophos, fenamiphos, chlorpyrifos, phorate, bispyribac, parathion, methyl parathion, methamidophos, fenamiphos, nitrate Anthomyl, dichlorvos, baclofos, monocrotophos, dibromophos, terpene, fruit phos, butylfenthion, ethyl ester phos, chloroxyphos, chloromethylthion, tianlephos, monothiotianlephos, dithiotianlephos, demeton, methyl demeton, sulfone, fenpropiphos, isothioate, chlorpyrifos, methyl ethyl ester phos, isosulfoxide, sulfone, chlorpyrifos, fenpropiphos, thiophos, thiophos, thiophos, anthiophos, oxathion Fruit, thiophos, thiophos, chlorpyrifos, methyl phoxim, methyl pyrifos, thiathion, oxathion, dichlorvos, chlorpyrifos, chlorpyrifos, pyraclofos, pyrifos, pyridazin, chlorimidophos, oxathion, zoleprox, pyraclofos, ethimphos, lilifus, pyrimidin, pyrimidin, methyl pyrimidin, thiathion, bromophos, ethyl bromophos, trithion, cypermethrin, cypermethrin, cypermethrin, isochlorophos, chloranthion ...Demeton-methyl, Isodeton-methyl, Amidophos, Temeton-O, Cypermethrin, Fospyraclofos, Oxfordshire Prothion, Ethyl Fenthion or Benoxaphos, Cypermethrin, Lambda-cyhalothrin, Cypermethrin, Cypervalerate, Cyfluthrin, Cyfluthrin, Lambda-cyhalothrin, Cyfluthrin, Bifenthrin, Deltamethrin, Acryloyl-cyhalothrin, Cis-cypermethrin, Bioresmethrin, Lambda-cyhalothrin, Permethrin, Fluvalinate, Allethrin, Bioallethrin, Cypermethrin, Lambda-cyhalothrin, Lambda-cyhalothrin, Zeta-cypermethrin, Cyphenothrin, Dextromethorphate, Esfenvalerate, Cypermethrin, Cypermethrin, Metofluthrin, Transfluthrin, Allethrin, Phenothrin, Benzylfluan Pyrethrin, biofluthrin, cis-fluthrin, tefluthrin, tetramethrin, tetrafluthrin, tralomethrin, beta-cypermethrin, ether cypermethrin, transfluthrin, S-bioallethrin, bromethrin, bromothrin, bromothrin, benzylthrin, chlorfenapyr, cyclic pyrethrin, cyhalothrin, beta-cyhalothrin, permethrin, D-trans-chlorfenapyr, pentafluoromethrin Permethrin, cypermethrin, S-cypermethrin, ... Permethrin, fluvalinate, pyrethroid, fenfluramine, cypermethrin, trans-permethrin, flumethrin, ethamethrin, DDT, methoxy-DDT, imidacloprid, thiamethoxam, acetamiprid, dinotefuran, clothianidin, nitenpyram, thiacloprid, chlorothiazolin, flonicamid, cypermethrin, sulfone cypermethrin, flupyrazone, trifluanid, sulfoxaflor, avermectin, methyl avermectin benzoate, lepidomicin, milbemycin, methoprene, methoprene, pyriproxyfen, fenoxycarb, clofenazine, flumethrin, hexathiazolin, etoxazole, matrine, azadirachtin, Bacillus thuringiensis, Beauveria bassiana, allicin, neonicotinoids, carvacrol, d-limonene, nicotine, pronicotine, oxymatrine, pyrethrins, cinerulin I, cinerulin I, cinerulin Chrysanthemin II, pyrethrin I, pyrethrin II, quassin, cypermethrin-III, rotenone, ryanodine, cypermethrin, veratrine, Bacillus thuringiensis, Bacillus sphaericus, sanguinarine or triptolide, diafenthiuron, azoxatin, tricyclazone, fenbutatin, propargyl, trichloroacetic acid sulfone, cypermethrin, dinitrophenol, sulfluramid, sulfanilamide, cartap, Insect ring, diflubenzuron, diflubenzuron, lufenuron, hexaflumuron, diflubenzuron, triflumuron, flubenzuron, flufenoxuron, flufenoxuron, flufenoxuron, buprofezin, cyromazine, bistrifluan, chlorfluazuron, flufenoxuron, flufenoxuron, pyrifos, pyrifos, methoprene, methoprene, pyriproxyfen, methoprene, furanthiocarb, chlorfenapyr, methoxyfenozide,Tebufenozide, fenapyr, cyclofenazine, α-ecdysone, ecdysterone, fenpyroximate, precocious hormone I, precocious hormone II, juvenile hormone I, juvenile hormone II, juvenile hormone III, hydrazone, acequinoxaline, pyrimidifen, pyrimidifen, bifenazate, fenpyroximate, fenpyroximate, pyrimidifen, tebufenoxam, pyraclostrobin, tolfenpyrad, rotenone, indoxacarb, metaflumizone, spirodiclofen, spiromesifen, spirotetramat, spirodiclofen, ethyl methoxypiperidin, cytoxanil, pyrimidifen, butyl fluoride Mite ester, leflubut, chlorantraniliprole, flubendiamide, cyanamide, cyclic bromine cyclobendiamide, tetrachlorantraniliprole, flucyanamide, bromine cyclobendiamide, fluoxetine, cyprodinil, pymetrozine, indoxacarb, cyanamide, chlorfenapyr, difenthiuron, dipropylene glycol, alloamicin, closantel, copper cyclohexane, crotamiton, dixanthate, anti-mite azole, fenoxacin, fluoroquine, flupyfuranone, hydrazone, sulfinamide, tebuconazole, flufenacet, trichlorfon, trichlorfon Ester, pyridaben, trifluoromethylpyrifos, flubendiquin, rafuxan, thuringin, benzyl thiazolin, triazolam, bromoacetamide, copper sulfate, ferric phosphate, metaldehyde, molluscicide, sodium pentachlorophenol, pyrrole nitrile, tributyltin oxide, molluscicide, nitropropenol, nitrophenol, dinitrophenol, oxadiazine, chlormequat, phosmet, pyrimidine, pyrimidine, cypermethrin, sanguinarine, spirotetramat, spiromesifen, thiamethoxam, thiabendazole, thiabendazole, triflumuron, fluazifop, sulfuron, Maltodextrin, boric acid, diatomaceous earth, silica gel, triphenyltin, borax, lime sulfur, copper oleate, mercurous chloride, potassium thiocyanate, sodium thiocyanate, chlordane, endosulfan, ethiprole, fipronil, spinosad, spinetoram, pymetrozine, pyrifoquinoxaline, diprofenopitide, amitraz, flonicamid, toluidine, flupentixol, isoxazole, fluazifop, nicotine, cypermethrin, imidacloprid, oxazolidinone, thiabendazole, methylphenidate, benzopyran, or dichlorothiazol.

[0035] Further, component B is selected from the following substances: profenofos, triazophos, malathion, phoxim, chlorpyrifos, ethiprole, fipronil, chlorfenapyr, bifenthrin, cypermethrin, chlorflucythrin, beta-cypermethrin, imidacloprid, acetamiprid, thiamethoxam, clothianidin, dinotefuran, nitenpyram, flupyradone, sulfoxaflor nitrile, triflubenzuron, abamectin, methyl avermectin, pyriproxyfen, pymetrozine, bicyclanil, diafenthiuron, triazotin, spirotetramat, tolfenpyrad, rotenone, indoxacarb, chlorantraniliprole, flubendiamide, cyanamide, cyclic bromofenapyr, tetrachlorantraniliprole, flucyanamide, tetrazolyl wormamide, flonicamid, bromofenapyr, flufenacil, fluoxametamide, isoxazole wormamide (Isocycloseram) or cyclopropylflufenacil.

[0036] Furthermore, the formulation of the insecticide and acaricide composition is selected from a suspension concentrate, a soluble granule, a suspension seed dressing agent, a granule, a microgranule or a water-dispersible granule.

[0037] Furthermore, the suspending agent is selected from a water-based suspending agent or an oil-based suspending agent.

[0038] Furthermore, the water-based suspension concentrate has a weight percentage of the crystalline form of Compound A between 1% and 50%, and further includes a weight percentage of a dispersant between 1% and 20%, a weight percentage of a wetting agent between 1% and 20%, a weight percentage of a thickener between 0.01% and 10%, a weight percentage of a preservative between 0.01% and 10%, a weight percentage of an antifreeze between 1% and 20%, and the balance being water.

[0039] Furthermore, the dispersant is selected from at least one of styrylphenol polyoxyethylene ether ammonium phosphate, tristyrylphenol polypropylene polyethylene block polyether, sodium salt, calcium salt or ammonium salt of lignin sulfonic acid (optionally polyethoxylated), sodium salt or ammonium salt of maleic anhydride copolymer, sodium salt of condensed phenol sulfonic acid, ammonium salt of polyarylphenyl ether sulfate or naphthalenesulfonate formaldehyde condensate; preferably at least one of styrylphenol polyoxyethylene ether ammonium phosphate and tristyrylphenol polypropylene polyethylene block polyether.

[0040] Furthermore, the wetting agent is selected from at least one of isomeric tridecanol polyoxyethylene ether, alkyl sulfosuccinates, laurates, alkyl sulfates, phosphates, acetylenic glycols, ethoxylated fluorinated alcohols, ethoxylated silicones, alkylphenol ethoxylates, benzenesulfonates, alkyl-substituted benzenesulfonates, alkyl α-olefin sulfonates, naphthalenesulfonates, alkyl-substituted naphthalenesulfonates, naphthalenesulfonates or condensates of alkyl-substituted naphthalenesulfonates and formaldehyde, 2-ethylhexyl glycol ether or alcohol ethoxylates; preferably isomeric tridecanol polyoxyethylene ether.

[0041] Furthermore, the thickener is selected from at least one of magnesium aluminum silicate, guar gum, pectin, casein, carrageenan, xanthan gum, alginate, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose, preferably at least one of magnesium aluminum silicate or xanthan gum.

[0042] Furthermore, the preservative is selected from derivatives of isothiazolone, preferably 1,2-phenylisothiazoline-3-one.

[0043] Furthermore, the antifreeze agent is selected from liquid polyols, preferably ethylene glycol, propylene glycol or glycerol.

[0044] In a fourth aspect, the present invention further provides a use of the above-mentioned crystal form of Compound A or the above-mentioned insecticide and acaricide composition in controlling insect pests and acarid pests, wherein the crystal form is selected from crystal form I, crystal form II, crystal form II or crystal form IV.

[0045] The present application provides a crystal form of compound A with excellent thermal storage stability, which is easy to store as a water suspension agent, has low water separation rate, high suspension rate, and good formulation flowability. At the same time, the product particle size reaches the nanometer level, the adhesion to leaves and pest mites is better under the small scale effect, the drug retention amount is higher, the penetration absorption is faster due to the small particle size, the drug effect is more rapid, and the rainwater washing resistance is high. Compared with amorphous, the melting point of the crystal form is improved. BRIEF DESCRIPTION OF DRAWINGS

[0046] Figure 1 is an X-ray powder diffraction of crystal form I;

[0047] Figure 2 is an X-ray powder diffraction of crystal form II;

[0048] Figure 3 is an X-ray powder diffraction of crystal form III;

[0049] Figure 4 is an X-ray powder diffraction of crystal form IV. DETAILED DESCRIPTION

[0050] The following examples can enable those skilled in the art to more fully understand the present application, but the present application is not limited in the scope of the described examples.

[0051] XRPD determination method

[0052] Instrument model: Bruker D 8 advance, target: Cu Kα (40 kV, 30 mA), sample to detector distance: 30 cm, scanning range: 5-40° (2θ value), scanning step: 0.12 s.

[0053] Example 1 Preparation method of compound A

[0054] 4-acetyl-2-methylbenzoic acid (1.97 g, 10 mmol) was added to 8 ml of toluene, and then sulfurous chloride (1.43 g, 12 mmol), N,N-dimethylformamide (0.1 ml) were added in sequence. The system was warmed to reflux for 5 h, and then the sulfurous chloride was removed under reduced pressure and transferred to a dropping funnel.

[0055] Another 100 ml three-necked flask was prepared, 10 ml of toluene, 3- aminocyclobutyl sulfone hydrochloride (2.58 g, 15 mmol), triethylamine (3.54 g, 35 mmol) were added in sequence, and the above acyl chloride solution was added dropwise under temperature control <60℃. After dropping, the temperature was controlled at 60℃ for 5 h, the system was cooled to <5℃ for crystallization, and then filtered and dried to obtain 2.6 g of light yellow solid.

[0056] Into 10 ml of dichloroethane, 4-acetyl-N-(l,l-dioxotetrahydrothiophen-3-yl)-2- methylbenzamide (1.48 g, 5 mmol) was added, followed by 3,5-dichloro-4-fluoro- trifluorophenylacetylacetone (2.07 g, 7.92 mmol), triethylamine (0.53 g, 5.28 mmol), potassium carbonate (0.36 g, 2.64 mmol), and the system was warmed to 50 °C for 8 h. After cooling to <10 °C, the system was filtered and dried to obtain 2.3 g of off-white solid.

[0057] Into 10 ml of dichloroethane, (Z)-4-(3-(3,5-dichloro-4-fluorophenyl)-4,4-4- trifluorobut-2-enyl)-N-(l,l-dioxotetrahydrothiophen-3-yl)-2-methylbenzamide (2.3 g, 4.28 mmol) was added, followed by tetrabutylammonium bromide (0.41 g, 1.28 mmol), aqueous hydroxylamine hydrochloride (0.45 g, 6.42 mmol), and the system was cooled to 0-5 °C. After adding aqueous sodium hydroxide (0.75 g, 18.83 mmol) dropwise while maintaining the temperature at <5 °C, the system was incubated for 8 h. After extracting the system with water twice, the organic phase was dried and concentrated to obtain 2.06 g of light yellow solid. The solid was subjected to X-ray powder diffraction to determine that it was amorphous.

[0058] Example 2

[0059] Into a 100 ml round bottom flask, 0.5 g of Compound A was added, followed by 10 mL of methanol. The system was heated and stirred in a 40 °C water bath for 3 h, and then filtered. The filtrate was allowed to stand for 4 days to volatilize the solvent, and the precipitated solid was filtered, washed, and dried to obtain white crystalline powder at a yield of 55.5% and a purity of 98.29%. The melting point was 224.53-225.68 °C. The X-ray powder diffraction pattern of the solid is shown in FIG. 1, and the data are shown in Table 1. The solid was named as Form I.

[0060] Table 1. X-ray powder diffraction data of Form I (methanol)

[0061] Example 3

[0062] Into a 100 ml round bottom flask, 0.5 g of Compound A was added, followed by 10 mL of acetonitrile. The system was heated and stirred in a 50 °C water bath for 3 h, and then filtered. The filtrate was allowed to stand for 7 days to volatilize the solvent, and the precipitated solid was filtered, washed, and dried to obtain white crystalline powder at a yield of 65.3% and a purity of 99.19%. The melting point was 226.15-227.79 °C. The X-ray powder diffraction pattern of the solid is shown in FIG. 2, and the data are shown in Table 2. The solid was named as Form II.

[0063] Table 2 X-ray powder diffraction data of Form II (acetonitrile)

[0064] Example 4

[0065] 0.5 g of Compound A was placed in a 100 ml round-bottom flask. 10 mL of acetone was added to the drug substance powder. The mixture was heated and stirred in a 45°C waterbath for 3 hours, then filtered. The filtrate was allowed to stand for 3 days to evaporate the solvent. The precipitated solid was filtered, rinsed, and dried to obtain a white crystalline powder with a yield of 78.2% and a purity of 99.23%. The melting range was 227.82-228.92°C. The X-ray powder diffraction pattern of this solid is shown in Figure 3, and the data are shown in Table 3. It is designated Form III.

[0066] Table 3 X-ray powder diffraction data of Form III (acetone)

[0067] Example 5

[0068] 0.5 g of Compound A was placed in a 100 ml round-bottom flask. 10 mL of ethyl acetate was added to the API powder. The mixture was heated and stirred in a 42°C waterbath for 3 hours, then filtered. The filtrate was allowed to stand for 7 days to evaporate the solvent. The precipitated solid was filtered, rinsed, and dried to obtain a white crystalline powder with a yield of 70.5% and a purity of 99.90%. The melting range was 226.69-228.91°C. The X-ray powder diffraction pattern of this solid is shown in Figure 4, and the data are shown in Table 4. It is designated Form IV.

[0069] Table 4 X-ray powder diffraction data of Form IV (ethyl acetate)

[0070] Example 6

[0071] 0.5 g of an amide-containing isoxazoline API was placed in a 100 ml round-bottom flask. 10 ml of ethanol was added to the API powder, and the mixture was heated and stirred in a 48°C waterbath for 3 hours before filtration. The filtrate was allowed to stand for 7 days to evaporate the solvent. The precipitated solid was filtered, rinsed, and dried to obtain a white crystalline powder with a yield of 51.2% and a purity of 99.31%. The melting range was 224.15-225.18°C. X-ray powder diffraction confirmed the product to be Form III.

[0072] Example 7

[0073] Put 0.5 g of compound A into a 100 ml round bottom flask, add 10 mL of dichloromethane to the raw material powder, heat and stir in a 30°C water bath for 3 h, then filter, let the filtrate stand for 2 days to volatilize the solvent, and then extract the precipitated solid by suction filtration, wash and dry to obtain a white powder with a yield of 85.2% and a purity of 98.15%. The melting range is 211.73-215.88°C. X-ray powder diffraction detection determines that it is amorphous.

[0074] Preparation of 10% compound A crystal form I-IV or amorphous water suspension

[0075] Add water and propylene glycol to a mixing tank, then add the adjuvants styryl phenol polyoxyethylene ether ammonium phosphate, triphenyl styryl phenol polypropylene polyethylene block polyether, isomeric tridecanol polyoxyethylene ether, mix well until the adjuvants are completely dissolved, then add the compound A crystal form sample and magnesium aluminum silicate, use a high-speed shearing machine to shear and homogenize the material, then transfer the material to a horizontal nanometer sand mill for circulation grinding. Use a laser particle size analyzer to monitor the particle size of the material, and when the particle size reaches D 90 <800 nanometers, discharge the material, then add xanthan gum mother liquor and BIT for viscosity adjustment. After the operation is completed, 10% compound A sample water suspension is obtained, and the preparation product has good flowability. The components are shown in Table 5:

[0076] Table 5 Water suspension component table

[0077] Test Example 1: Heat storage experiment of water suspension

[0078] The water suspension sample prepared in Preparation Example 1 is packaged in an ampoule bottle and placed in an oven at a temperature of 54°C for 14 days, then the flowability of the suspension is observed, the water separation is detected, and the water separation rate, suspension rate and particle size are calculated. The data are compared before and after heat storage. The analysis test method is as follows:

[0079] Water separation rate determination: 10 mL of sample is injected into a calibrated ampoule bottle, sealed with an alcohol lamp, and placed in a (54±2) °C heat storage for 14 days. The total height of the sample and the height of the transparent water layer are observed, and the water separation rate is calculated according to the formula. Water separation rate = transparent water layer height / sample total height x 100%.

[0080] Suspension rate determination: 1 gram of the sample to be tested is added to 2000 grams of standard hard water to prepare a liquid. At room temperature, the sample is placed in a graduated cylinder for 30 minutes, and the active ingredient content in the bottom tenth of the suspension is measured to calculate the suspension rate.

[0081] Particle size determination: 0.5 mL of the suspension sample is added to the sample cell of the laser particle size analyzer, and the measurement is performed after ultrasonic dispersion for 1 minute, with 3 repeats for each treatment.

[0082] The experimental results are shown in Table 6 below.

[0083] Table 6 Thermal storage experimental results of 20% compound A crystal form I aqueous suspension

[0084] Under the same conditions, after 14 days of thermal storage, the products of crystal forms I, II and IV have lower water precipitation, higher fluidity, higher suspension rate, smaller particle size and no obvious change compared with crystal form III and amorphous form. The compound A crystal form I, II and IV aqueous suspension has excellent thermal storage stability.

[0085] Test Example 2 Tetranychus cinnabarinus activity test of aqueous suspension

[0086] Take 0.1 g of 10% compound A crystal form I-IV or amorphous aqueous suspension prepared in Preparation Example 1, add it to a 10 mL volumetric flask, add purified water to make up to 10 mL, and obtain 1000 mg / L of liquid medicine. Take 0.625 g of 1000 mg / L liquid medicine, add purified water to make up to 100 mL, and obtain 6.25 mg / L of liquid medicine. Dilute with water in turn to obtain the required test concentration of liquid medicine.

[0087] Remove one true leaf from the bean seedlings grown to two true leaves, inoculate Tetranychus cinnabarinus, and investigate the base number. Use a handheld sprayer to spray the whole plant, repeat 3 times for each treatment (the amount of formulation used is about 0.5 g), and observe in a constant temperature observation room after treatment. Investigate the number of live mites after 72 hours, and calculate the mortality rate. The experiment is repeated 3 times, and the number of Tetranychus cinnabarinus inoculated each time is 35-100.

[0088] Mortality rate (%) = (number of inoculated mites - number of live mites after treatment) ÷ number of inoculated mites × 100%.

[0089] Table 7 Tetranychus cinnabarinus activity test results of aqueous suspension

[0090] As can be seen from the test results in Table 7, the 10% compound A crystal form I-IV aqueous suspension all have excellent Tetranychus cinnabarinus killing activity, and the miticidal activity of the aqueous suspension prepared from the amorphous technical material is significantly improved.

Claims

1. A crystalline Form II of a five-membered heterocycle-containing compound having the structure of Formula A: ###00001### Formula A Form II exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 5.02, 11.88, 14.98, 15.02, 19.14, 19.16, 19.22, 19.24, 19.28, 19.36, 19.38, 19.40, 19.42, 19.46, 19.48, 19.5, 19.52, 19.54, 19.56, 19.58, 22.62, 27.00, 27.04, 27.06, 27.08, 27.10, wherein the error range in 2-theta is within ±0.2°.

2. The crystalline Form II of claim 1, characterized by, Form II exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 15.02, 19.42, 19.46, 19.48, 19.52, 22.62, 27.06, 27.10, wherein the error range in 2-theta is within ±0.2°; preferably, the Form II has an X-ray powder diffraction pattern as shown in Figure 2.

3. A crystalline Form I of a five-membered heterocycle-containing compound having the structure of Formula A: ###0001### Formula A Form I exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 5.32, 5.66, 11.92, 13.96, 14.1, 15.94, 16.96, 17.16, 18.54, 18.84, 19.08, 19.3, 19.38, 19.40, 19.44, 19.52, 20.14, 20.24, 21.42, 21.52, 22.74, 25.76, 27.58, 33.14, 34.48, wherein the error range in 2-theta is within ±0.2°.

4. The crystalline Form I of claim 3, characterized by, Form I exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 14.20, 17.28, 19.38, 19.40, 19.44, 20.24, 21.42, wherein the error range in 2-theta is within ±0.2°; preferably, the Form I has an X-ray powder diffraction pattern as shown in Figure 1.

5. A crystalline Form III of a five-membered heterocycle-containing compound having the structure of Formula A: ###0001### Formula A Form III exhibits at least three of the following diffraction peaks, given in degrees of 2-theta, in an X-ray powder diffraction pattern: 5.80, 6.72, 10.66, 11.94, 13.68, 16.28, 17.56, 19.18, 19.36, 19.44, 19.48, 19.50, 20.68, 21.24, 21.36, 21.42, 22.54, 23.66, 25.00, 27.00, 27.70, 29.46, 31.56, wherein the error range in 2-theta is within ±0.2°.

6. The crystalline Form III of claim 5, characterized by, The crystal form III shows at least three of the following diffraction peaks given in 2θ values in an X-ray powder diffraction pattern: 17.56, 19.18, 19.36, 19.44, 19.48, 19.50, 21.36, 21.42, 22.54, 25.00, 27.70, wherein the error range of the 2θ values is ±0.2°; preferably, the crystal form III has an X-ray powder diffraction pattern as shown in Figure 3.

7. A crystalline Form IV of a five-membered heterocycle-containing compound having the structure of Formula A: ###0001### Formula A The crystal form IV shows at least three of the following diffraction peaks given in 2θ values in an X-ray powder diffraction pattern: 5.68, 7.28, 11.90, 15.04, 17.40, 17.54, 19.12, 19.26, 19.34, 19.40, 19.42, 19.50, 21.32, 21.40, 22.66, 26.92, 27.66, 31.54, wherein the error range of the 2θ values is ±0.2°.

8. The crystalline Form IV of claim 7, characterized by, The crystal form IV shows at least three of the following diffraction peaks given in 2θ values in an X-ray powder diffraction pattern: 11.90, 17.54, 19.26, 19.34, 19.40, 19.42, 19.50, 26.92, 27.66, wherein the error range of the 2θ values is ±0.2°; preferably, the crystal form IV has an X-ray powder diffraction pattern as shown in Figure 4.

9. A process for preparing a crystalline form of a five-membered heterocycle containing compound having the structure of Formula A: ###0001### Formula A 1) dissolving compound A in a solvent, filtering after heating and stirring; 2) standing the filtrate for a period of time to volatilize the solvent, and drying the solid precipitated by suction filtration, to obtain the crystal form of compound A.

10. The method of claim 9, wherein, The solvent in step 1) is selected from at least one of petroleum ether, methanol, ethanol, isopropanol, n-propanol, t-butanol, ethylene glycol, 1,2-propanediol, dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, ethyl acetate, toluene, xylene, acetonitrile, tetrahydrofuran, dioxane, methyl t-butyl ether, acetone, methyl isobutyl ketone, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or water; and / or, the heating temperature in step 1) is selected from 30-50°C; and / or, the standing time in step 2) is 3-7 days.

11. An insecticidal and miticidal composition containing the crystal form of the compound having the five-membered heterocyclic ring according to any one of claims 1-8, the weight percentage content of the crystal form being 1%-50%, and the crystal form being selected from the crystal form I, the crystal form II, the crystal form III or the crystal form IV.

12. The insecticidal and miticidal composition according to claim 11, wherein The insecticidal and acaricidal composition further comprises component B in an amount of 1 to 50% by weight, wherein component B is selected from the group consisting of profenofos, triazophos, malathion, phoxim, chlorpyrifos, ethiprole, fipronil, chlorfenapyr, bifenthrin, cypermethrin, lambda cyhalothrin, beta-cyfluthrin, imidacloprid, acetamiprid, thiamethoxam, clothianidin, dinotefuran, nitenpyram, flupyradifurone, sulfoxaflor, triflumuron, abamectin, milbemycin, pyridalyl, pymetrozine, dihydropyrifluorene, clofentezine, hexythiazox, chlorfenapyr, indoxacarb, sulfoxaflor, flubendiamide, cyantraniliprole, cycloxaprid, tetrachloraniliprole, fluoranilide, tetraniliprole, flonicamid, broflanilide, fluxametamide, isocycloseram, or cycloprothrin.

13. The insecticidal and miticidal composition according to claim 11, wherein The insecticidal and acaricidal composition is in a dosage form selected from the group consisting of a suspension concentrate, a water soluble granule, a suspension seed dressing, a granule, a microgranule, or a water dispersible granule; preferably a water based suspension concentrate or an oil based suspension concentrate.

14. Use of the crystal form according to any one of claims 1 to 8 or the insecticidal and acaricidal composition according to any one of claims 11 to 13 for controlling insect pests or acarid pests.

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