CN118930463A - A new crystal form of trifluoroethyl sulfide compound, preparation method thereof, insecticide and acaricide composition and application thereof - Google Patents

A new crystal form of trifluoroethyl sulfide compound, preparation method thereof, insecticide and acaricide composition and application thereof Download PDF

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CN118930463A
CN118930463A CN202310517154.7A CN202310517154A CN118930463A CN 118930463 A CN118930463 A CN 118930463A CN 202310517154 A CN202310517154 A CN 202310517154A CN 118930463 A CN118930463 A CN 118930463A
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methyl
phosphorus
chlorpyrifos
crystal form
insecticidal
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Inventor
祝青波
盛国柱
李海洋
孙攀
许垠
项效忠
刘祥伟
刘军伟
段金乐
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Shandong Kangqiao Bio Technology Co ltd
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Shandong Kangqiao Bio Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom not containing sulfur-to-oxygen bonds, e.g. polysulfides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/26—Separation; Purification; Stabilisation; Use of additives
    • C07C319/28—Separation; Purification

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Insects & Arthropods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to a novel crystal form of a trifluoroethyl thioether compound, a preparation method thereof, an insecticidal and acaricidal composition and application thereof, and belongs to the technical field of crystal forms. The trifluoroethyl thioether compound is methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate, and in an X-ray diffraction spectrum under Cu-Ka radiation, X-ray powder diffraction represented by a diffraction angle 2 theta mainly has characteristic peaks as follows: 12.0 ° ± 0.2 °,13.4 ° ± 0.2 °,24.8 ° ± 0.2 °. The crystal form provided by the invention has high stability and is easy to store. The insecticidal and acaricidal composition prepared from the novel crystal form has the advantages of good physical stability, high-temperature and low-temperature storage resistance, difficult caking and delamination, good adhesiveness to leaves and mites under the small-scale effect, and higher liquid medicine retention. The particle size is small, the permeation and absorption are faster, and the drug effect is quicker. The rain wash resistance is improved by more than one time compared with the common products.

Description

New crystal form of trifluoroethyl thioether compound, preparation method thereof, insecticidal and acaricidal composition and application thereof
Technical Field
The invention relates to the technical field of crystal forms, in particular to a novel crystal form of trifluoroethyl thioether compounds, a preparation method thereof, an insecticidal and acaricidal composition and application thereof.
Background
Pest mites are one of important factors causing yield reduction of crops such as oranges, flowers, vegetables and the like and cash crops, and are mostly gathered on the back of leaves, and adults and nymphs pierce the leaves with mouthparts to suck juice, so that leaf green elements of landscape plants are often damaged, and photosynthesis is affected. In severe cases, the leaves die and fall off, even the plants die due to She Pianla light. In addition, many mites also spread plant viral and fungal diseases. Therefore, the development of efficient and environment-friendly insecticidal and acaricidal agents is an important subject to be continuously researched in the pesticide field. The trifluoroethyl thioether pesticide has excellent insecticidal and acaricidal activity and is environment-friendly, and has become an important direction in the field of research and development of insecticidal and acaricidal agents.
The patent WO2021056922 discloses a preparation method of methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate (compound A) and application thereof as an insecticidal acaricide. The specific structure is as follows:
。
According to the preparation method disclosed in patent WO2021056922, after the reaction is finished, the reaction solution is added into water, then extracted with ethyl acetate, washed with water, dried, concentrated to dryness under reduced pressure, then purified by column chromatography, and the solvent is evaporated to dryness to obtain methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate (compound a). The obtained methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate (compound A) is in an amorphous state, and cannot be prepared into a dosage form with good performance, so that the effect of large-scale application is affected.
Disclosure of Invention
Aiming at the technical problems that the existing methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate is in an amorphous state and cannot be prepared into a dosage form with good performance, the invention provides a novel crystal form of the methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate, a preparation method thereof, an insecticidal and acaricidal composition and application of the crystal form in controlling insect and acarid pests.
In a first aspect, the invention provides a crystalline form i of methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate (compound a), having a characteristic peak at a diffraction angle 2θ of 12.0 ° ± 0.2 °,13.4 ° ± 0.2 °,24.8 ° ± 0.2 ° in an X-ray diffraction pattern under Cu-Ka radiation.
Further, in the X-ray diffraction pattern of the crystal form I under Cu-Ka radiation, the diffraction angle 2 theta has characteristic peaks at 12.0 degrees+/-0.2 degrees, 13.4 degrees+/-0.2 degrees, 24.8 degrees+/-0.2 degrees, 18.2 degrees+/-0.2 degrees, 19.1 degrees+/-0.2 degrees, 23.3 degrees+/-0.2 degrees, 20.1 degrees+/-0.2 degrees, 22.2 degrees+/-0.2 degrees and 29.2 degrees+/-0.2 degrees.
Further, in the X-ray diffraction pattern of the crystal form I under Cu-Ka radiation, the diffraction angle 2 theta has a characteristic peak at 10.9±0.2°,12.0±0.2°,13.4±0.2°,18.2±0.2°,18.6±0.2°,19.1±0.2°,19.6±0.2°,20.1±0.2°,20.8±0.2°,21.1±0.2°,22.2±0.2°,23.3±0.2°,24.0±0.2°,24.2±0.2°,24.8±0.2°,25.2±0.2°,26.1±0.2°,26.6±0.2°,26.9±0.2°,27.6±0.2°,29.2±0.2°,30.1±0.2°,32.1±0.2°,34.1±0.2°,36.5±0.2°,39.6±0.2°.
In a second aspect, the invention provides a preparation method of the compound A crystal form I, which comprises the following steps:
(1) Under heating, dissolving the amorphous compound A in a single solvent or a mixed solvent;
(2) Precipitating the dissolved compound A into a compound A crystal form I under the condition of cooling;
(3) Separating and precipitating to obtain the crystal form I of the compound A.
Further, the solvent is at least one selected from petroleum ether, methanol, ethanol, isopropanol, propanol, butanol, ethylene glycol, 1, 2-propylene glycol, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, ethyl acetate, toluene, xylene, acetonitrile, tetrahydrofuran, dioxane, methyl tertiary butyl ether, acetone, methyl isobutyl ketone, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or water.
In a third aspect, the invention provides an insecticidal and acaricidal composition containing the compound A crystal form I, wherein the weight percentage of the crystal form I is 1% -50%.
Further, the insecticidal and acaricidal composition also comprises a component B, wherein the weight percentage of the component B is 1% -50%; the insecticidal and acaricidal composition also comprises an agriculturally or forestry acceptable auxiliary agent or carrier.
Further, component B is selected from the following: isoprocarb, carbosulfan, benfuracarb, carbosulfan, methomyl fenobucarb, methomyl, propoxur, fenoxycarb, oxacarb, carbaryl, carbofuran, and their use in the preparation of pharmaceutical compositions fenobucarb, methomyl, propoxur fenoxycarb, oxacarb, carbaryl, carbofuran mixed carbofuran, methomyl, phoxim, dimemamectin benzoate, chlorpyrifos isoxacarb, pyrimidyl, pyrazolocarb, aldicarb, pentofacicarb, thiamethoxam isoxacarb, pyrimidyl, pyrazolocarb aldicarb, pentoficarb, thiamethoxam, Carbofuran (decarbofuran), carbofuran (thiocarboxime), dicranyl (dicresyl), carbofuran (hyquincarb), clofenamic (carbanolate), chlorpyrifos-methyl, triazophos, phoxim, profenofos, thioprop, methidathion, fenitrothion, malathion, valphos, diazinophos, phoxim, pyraclos, pyridaphethione, imiphos, quinalphos (quintiofos), acephate, methiphos, isopisphorphos, oxazophos, pyraclos, butyl pyrimidine phosphorus, phenthoate, fenitrothion, terbutafos, aphos, dimethoate, omethoate, chlorpyrifos, fos, dibromo-phosphorus, fast-moving phosphorus, triclopyr, dichlorvos, aminopropphos, chlorpyrifos, thiophos, paraquat, methylprotophos, profos, sulfoxide phosphorus, heptenophos, napeptidos, house fly phosphorus, coumaphos, ethahos, methyl-ethyl, ethios, acephate, chlorzophos, yigossyp, bazophos, valvafos, cartap, methiphos, parathion, methyl-parathion, benfophos, nitrophos, dichalcium, baduphos, monocrotophos, terpran, Fruit phosphorus, styrene-butadiene phosphorus, ethyl ester phosphorus, chlorpyrifos, chloromethyl phosphorus, tian Le phosphorus, monothio Tian Le phosphorus, dithio Tian Le phosphorus, endo phosphorus, methyl endo phosphorus (demeton-methyl), sulfone phosphorus, feng Bing phosphorus, isomix phosphorus, chlorfenphos, methyl ethyl ester phosphorus, isosulfoxide phosphorus, sulfone phosphorus, cyphos, fruit worm phosphorus, yi-sulfur phosphorus, an-sulfur phosphorus, sulfur-emitting phosphorus, su Liu phosphorus, chlorooctphos, methyl octyl phosphorus, methyl pyrifos, thiazole phosphorus, animal phosphorus, dixyl phosphorus, cloisonne phosphorus, cyclopentadienyl phosphorus, pyrifos, chlorimtiaphos, oxazolphosphorus, zoliprone (zolaprofos), pyrazophos, ethionine phosphorus, Li Lifu S (lirimfos), pyrimidophos, methylpyrimidophos, fosthiazate, thiophos-bromate, ethylthiophos-bromate, trithiophos, chlorpyrifos, fenitrothion, trichlorphos, cyromazine, fenitrothion, iodiphos, phoxim sulfoxide (mesulfenfos), fenthion, butyl phosphine Tetramethylphosphine, dinotefuran, chlorpyrifos, cyanophenyl phosphine, bromophenyl phosphine, livestock raising phosphorus, butylthiocyclophosphorus, dinotefuran, thiocyclophosphorus, methylsulfothiocyclophosphate, chloramine phosphorus, chlorpyrifos amifos, methyl isosalazine, glycifos, meflofos propylamine fluorophosphine, octamethylphosphine, triphosphine tin, bromophenphosphorus (bromofenvinfos), Azido (mazidox), methamidophos (pirimiphos), ethionas (prothidathion), azophos (azothoate), O- {2- [ acetyl (ethyl) amino ] -6-methyl-4-pyrimidinyl } O, O-diethyl thiophosphate (primidophos), azophos (pyrimitate), mequinothiol (quinalphos-methyl), methidathion (athidathion), p-chlorthion (phosnichlor), le Naisong-3 (trichlormetaphos-3), Triflosone (trifenofos), quinocetone (quinothion), thiopyran phosphorus (dithicrofos), sulfur Liu Lin (thicrofos), methyl isoamyl (demeton-O-methyl), amine phosphorus (amiton), termidothiophos (butathiofos), endophos-O (demeton-O), chlorpyr-diethyl phosphate (chlorprazophos), pyrifos-methyl (fospirate), oxforn propyl phosphorus (etaphos), ethyl thiophos (fenthion-methyl), benoxaphos (benoxafos), cypermethrin, lambda-cyhalothrin, fenpropathrin fenvalerate, fenfluramine, fenvalerate, fenfluramine, fenvaler fenvalerate, fenvalerate cyhalothrin, high-efficiency cyhalothrin cyfluthrin (fluvalinate), allethrin, bioallethrin, fenpropathrin refined efficient cyhalothrin, efficient trans-cyhalothrin refined high-efficiency cyhalothrin high-efficiency trans-cypermethrin, Tetramethrin, propathrin, phenothrin, bifenthrin, biothrin, bifenthrin, and bifenthrin cis-bifenthrin, tefluthrin, tetramethrin, tefluthrin cis-bifenthrin, tefluthrin tetramethrin, tetrafluorotetramethrin permethrin, cyclothrin, cyhalothrin, permethrin, fenpropathrin, fenhexamid, fenpyroximate, D-trans-permethrin, pencythrin, cyhalothrin, S-fenvalerate dextro-trans-prallethrin, penfluthrinate Cyhalothrin, S-fenvalerate, fenvalerate, fenpropithrin, deltamethrin, valerate, trifluorethrin, fenacet, fentanyl propionate (protrifenbute), silafluofen (silafluofen), thiooxime ether, thiofluoroxime ether, flumethrin, fumaghemite (barthrin), benfurin (bioethanomethrin), prallethrin (furethrin), tefluthrin (heptafluthrin), trans-permethrin (TRANSPERMETHRIN), profenothrin (profluthrin), pyrimethamine (PYRESMETHRIN), The composition comprises the following components of D, P-D, imidacloprid (dimpropyridaz), thiamethoxam, acetamiprid, dinotefuran, clothianidin, nitenpyram, thiacloprid, chlorthialine, flonicamid, piprolin, sulfluramid, flupyrad-idone (flupyradifurone), trifluralin, fipronil, abamectin, methyl abamectin benzoate, lepidomycin, milbemycin, nitenpyram, methoprene, pyriproxyfen, tetramethrin, flufenzine, hexythiazox, etoxazole, matrine, nimbin, bacillus thuringiensis, Beauverine, garlicin, neonicotine, carvacrol, d-limonene, nicotine (nicofluprole), primordial nicotine, oxymatrine, pyrethrin, guathrin I (cinerins), gualasin I, gualasin II, heliothin I, heliothin II, pyrethrin I, pyrethrin II, quassia (quassia), azalide-III, rotenone, ryanidine (ryania), resveratrol, bacillus sphaericus, sanguinarine, triptolide, diafenthiuron, azocyclotin, tricyclin, fenbutatin, propargite, chlorfenapyr, dinitrilol, flufenamid, Polyfluorourea, fluoroureide, flufenoxuron flucycloxuron, buprofezin, cyromazine, chlorpyrifos, polyfluorourea, fluoroureide, flufenoxuron, flucycloxuron, buprofezin, cyromazine, and the like bistriflumuron, chlorfluazuron, epoxiconamide pyridazinone, juvenile ether (epofenonane), methoprene, furtebufenozide, chlortebufenozide, methoxyfenozide, tebufenozide, antifebrile, chromafenozide, alpha ecdysone, ecdysterone, benomyl, precocin I, precocin II, procyanidin I (juvenile hormone I), procyanidin, and procyanidin, Juvenile hormone II (juvenile hormone II), juvenile hormone III (juvenile hormone III), flumizone, chlorfenapyr, pyriminostrobin, bifenazate, fenpyroximate, pyriminostrobin, tebufenpyrad, pyridaben, tolfenpyrad, indoxacarb, metaflumizone, spirodiclofen, spiromesifen (spiromesifen), spirotetramat, spirodiclofen, methoprene (spiropidion), ethionazole, cyenopyrafen, cyflumetofen, leflunomide (pyflubumide), chlorantraniliprole, flufenamid, fenbufenpyrad, Cyantraniliprole, cycloxapride, tetrachlorethamide, flucyantraniliprole, tetrazolium, brofil-bezamide (brofilide), fluxapyroxad (fluxametamide), cyproconazole, pymetrozine, chlorfenapyr, dipropionate (afidopyropen), alommonemulin (allosamidin), chlorphenamine, copper naphthenate (copper naphthenate), crotamiton, dixanthogen, fenbuconazole, fenoxacin (fenoxacrim), fluoroquin (flometoquin), Metaflumizone, tebufenpyrad, trifluralin, triclosan, trifluoperazone, flubenflumizone, lei Fusha-naphthalene, thuringiensis, fenpropineb, triazamate, bromoacetamide, copper sulfate, ferric phosphate (ferrophosphorus), metaldehyde, niclosamide, sodium pentachlorophenate, pyrronitrile (tralopyril), tributyltin oxide, spironoline, nitroprusside (dinoprop), penta-nitrophenol, oxadiazon, pyriminode, bupropion, chlorfenapyr (flucofuron), trifluramide (sulcofuron), trifluouron (sulcofuron), Maltodextrin, boric acid, diatomite (diatomaceous earth), silica gel, triphenyltin, borax (borax), lime sulphur, copper oleate (copper oleate), mercurous chloride (mercurous chloride), potassium thiocyanate (potassium thiocyanate) sodium thiocyanate (sodium thiocyanate), chlordane, endosulfan, ethiprole, fipronil, spinosad, spinetoram, praziquantel, amitraz, venomous dragon (Acynonapyr), norfloxacin (flupentiofenox), isoxazolidinamide (Isocycloseram), fluoropyrimidine (flupyrimin), cyclo Ding Fulun (cyclobutrifluram), oxazolothio (oxazosulfyl), thiabendazole (tyclopyrazoflor), benzopyran (benzpyrimoxan), or dichlorothiazole (dicloromezotiaz).
Further, component B is selected from the following: profenofos, triazophos, malathion, phoxim, chlorpyrifos, ethiprole, fipronil chlorfenapyr, bifenthrin, fenpropathrin, cyhalothrin, lambda-cyhalothrin chlorfenapyr, bifenthrin, fenpropathrin cyhalothrin, lambda-cyhalothrin pyriproxyfen, pymetrozine, dicycloprid, diafenthiuron, azocyclotin, spirotetramat, tolfenpyrad, rotenone, indoxacarb, chlorantraniliprole, fipronil, cyantraniliprole, triamcinolone, chlorantraniliprole, triamcinolone, and other drugs Cyclochlorantraniliprole, tetrachlorethamide, flucyantraniliprole, tetrazolium-chlorantraniliprole, flonicamid, chlorantraniliprole, and chlorantraniliprole bromarol diamide, fluxapyroxad, isoxazole diamide or cyproconazole.
Further, the dosage form of the insecticidal and acaricidal composition is selected from suspending agents, soluble granules, suspension seed dressing agents, granules, particles or water dispersible granules.
Further, the suspending agent is selected from a water-based suspending agent or an oil-based suspending agent.
Further, in the water-based suspending agent, the weight percentage of the compound A crystal form I is 1% -50%, the water-based suspending agent further comprises a dispersing agent with the weight percentage of 1% -20%, a wetting agent with the weight percentage of 1% -20%, a thickening agent with the weight percentage of 0.01% -10%, a preservative with the weight percentage of 0.01% -10%, an antifreezing agent with the weight percentage of 1% -20%, and the balance of water.
Further, the dispersant is at least one selected from the group consisting of styrene methacrylic acid copolymer, styrene maleic anhydride copolymer, sodium or calcium salt or ammonium salt of lignin sulfonic acid (optionally polyethoxylated), sodium or ammonium salt of maleic anhydride copolymer, sodium salt of condensed phenol sulfonic acid, ammonium salt of polyarylphenyl ether sulfate, and naphthalene sulfonate-formaldehyde condensate; at least one of styrene methacrylic acid copolymer or styrene maleic anhydride copolymer is preferable.
Further, the wetting agent is selected from at least one of a blocked polyether, an alkyl sulfosuccinate, a laurate, an alkyl sulfate, a phosphate, an acetylenic diol, an ethoxylated fluorinated alcohol, an ethoxylated silicone, an alkylphenol ethoxylate, a benzenesulfonate, an alkyl-substituted benzenesulfonate, an alkyl alpha-olefin sulfonate, a naphthalenesulfonate, an alkyl-substituted naphthalenesulfonate, a naphthalenesulfonate or a condensate of an alkyl-substituted naphthalenesulfonate with formaldehyde, 2-ethylhexanoylpropylene glycol ether or an alcohol ethoxylate; block polyethers are preferred.
Further, the thickener is at least one selected from magnesium aluminum silicate, guar gum, pectin, casein, carrageenan, xanthan gum, alginate, methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose.
Further, the dispersing agent is at least one selected from magnesium aluminum silicate and xanthan gum.
Further, the preservative is selected from derivatives of isothiazolone; 1, 2-Benzisothiazolin-3-one is preferred.
Further, the antifreeze is selected from liquid polyols, preferably ethylene glycol, propylene glycol or glycerol.
In a fourth aspect, the invention also provides an application of the compound A crystal form I and/or the insecticidal and acaricidal composition in insect pest control.
The invention has the beneficial effects that:
The compound A crystal form I provided by the invention has high stability and is easy to store. The insecticidal and acaricidal composition prepared from the compound A crystal form I has good physical stability, high and low temperature storage resistance, difficult caking and delamination, the grain size of the product reaches the nanometer level, the adhesiveness to leaves and mites is better under the small scale effect, and the liquid medicine retention is higher. The particle size is small, the permeation and absorption are faster, and the drug effect is quicker. The rain wash resistance is improved by more than one time compared with the common products.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Figure 1 is an X-ray powder diffraction pattern of compound a form i.
FIG. 2 is an Infrared (IR) spectrum of form I of compound A.
FIG. 3 is a dynamic moisture adsorption Desorption (DVS) profile for Compound A form I.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
EXAMPLE 1 preparation of Compound A form I
According to the preparation method disclosed in patent WO2021056922, the amorphous compound A is obtained.
30G of compound A is weighed and placed in a 500mL round bottom flask in an amorphous way, 100mL of methanol is added, the mixture is heated and refluxed until the solid is dissolved under stirring, the temperature of the reaction flask is slowly reduced to 25 ℃ at room temperature, the solid is slowly separated out, the mixture is continuously stirred for 5 hours, then the mixture is decompressed and filtered, and the solid is dried and then weighing 24.6g. Melting point: 84 ℃.
The above product was subjected to X-ray powder diffraction analysis on an X' Pert 3X-ray powder diffractometer. The specific conditions are as follows:
X-ray light source: cu, K alpha
Kα1 (Å)：1.54060；Kα2 (Å)：1.54439
Kα2/kα1 intensity ratio: 0.50
Voltage: 45 kilovolts (kV)
Current flow: 40 milliamperes (mA)
Scanning range: from 3.0 to 40.0 degrees.
The X-ray powder diffraction pattern is shown in fig. 1, and the data are shown in table 1.
TABLE 1 preparation of X-ray powder diffraction data for Compound A form I
Infrared spectroscopy was performed on an FT-IR spectrometer. The specific conditions are shown in table 2 below.
TABLE 2 Infrared Spectrum conditions
The infrared spectrum is shown in FIG. 2, and the data are detailed in Table 3.
TABLE 3 preparation of IR spectrum data for Compound A form I example 1
The hygroscopicity analysis was performed on DVS INTRINSIC of SMS (Surface Measurement Systems). The specific conditions are shown in table 4 below.
Table 4 DVS conditions
Compound a form i and compound a amorphous dynamic moisture adsorption Desorption (DVS) curves were tested on DVS INTRINSIC of SMS (Surface Measurement Systems), the relative humidity at 25 ℃ was corrected with the deliquescence points of LiCl, mg (NO 3)2 and KCl), the experimental results are shown in table 5.
TABLE 5 Compound A Crystal form I and amorphous DVS results
According to the definition of drug hygroscopicity in Chinese pharmacopoeia 2020 edition, the compound A crystal form I belongs to the compound A with no or almost no hygroscopicity, can keep stable properties under the high-humidity condition, can keep stable without specific humidity control conditions in the production, storage and use processes, and can well meet the requirements of drug production and use.
Similar results can be obtained with other single solvents or mixed solvents instead of methanol.
EXAMPLE 2 preparation of 20% Compound A Crystal form I aqueous suspension
Adding water and propylene glycol into a mixing tank, adding an auxiliary agent of styrene methacrylic acid copolymer, styrene maleic anhydride copolymer and block polyether, fully mixing and stirring until the auxiliary agent is completely dissolved, adding a compound A crystal form I and magnesium aluminum silicate, shearing and homogenizing the materials by using a high-speed shearing machine, and transferring the materials into a horizontal nano sand mill for circular grinding. And monitoring the particle size of the material by using a laser particle sizer, discharging when the particle size reaches D90<800 nanometers, adding xanthan gum mother liquor and BIT for viscosity blending, and obtaining the 20% compound A crystal form I water suspending agent after the operation is finished, wherein the fluidity of the preparation product is good. The compositions are shown in Table 6 below:
TABLE 6 20% composition of Compound A Crystal form I aqueous suspension
Comparative example 1 preparation of 20% amorphous aqueous Compound A suspension
Adding water and propylene glycol into a mixing tank, adding an auxiliary agent of styrene methacrylic acid copolymer, styrene maleic anhydride copolymer and block polyether, fully mixing and stirring until the auxiliary agent is completely dissolved, adding an amorphous compound A and magnesium aluminum silicate, shearing and homogenizing the material by using a high-speed shearing machine, and transferring the material into a horizontal nano sand mill for cyclic grinding. And monitoring the particle size of the material by using a laser particle sizer, discharging when the particle size reaches D90<800nm, adding xanthan gum mother liquor and BIT for viscosity blending, and obtaining the compound A aqueous suspension in a 20% amorphous state after the operation is finished, wherein the fluidity of the preparation product is general. The compositions are shown in Table 7 below:
TABLE 7 20% amorphous aqueous suspension of Compound A Components Table
EXAMPLE 3 thermal storage test of aqueous suspension
The 20% aqueous suspension of compound a crystal form i and the 20% amorphous aqueous suspension of compound a prepared in example 2 and comparative example 1 were packaged in ampoule bottles, put into an oven, stored at 54 ℃ for 14 days, then the fluidity of the suspension was observed, the water evolution condition was detected, the water evolution rate, the suspension rate and the particle size were calculated, and the data were compared with those before heat storage. The analytical test method is as follows:
And (3) measuring the water separation rate: 10mL of the sample is injected into a graduated ampoule bottle, an alcohol burner is sealed, the sample is placed at the temperature of 54+/-2 ℃ for heat storage for 14 days, the total height and the transparent water layer height of the sample are observed, and the water separation rate is calculated according to a formula. Water evolution = clear water layer height/total sample height x 100%.
Suspension rate measurement: 1 g of suspending agent of a sample to be tested is added with standard hard water to dilute and prepare 2000 g of liquid medicine. And standing in a measuring cylinder for 30 minutes at room temperature for sampling, measuring the content of the active ingredients in the bottom tenth suspension, and calculating the suspension rate.
Particle size measurement: 0.5mL of the suspending agent sample was added to the laser particle sizer sample cell, and after 1 minute of ultrasonic dispersion, the measurement was performed, and each treatment was repeated 3 times.
The experimental results are shown in table 8 below:
TABLE 8 thermal storage test results for 20% Compound A Crystal form I aqueous suspension
Under the same conditions, after the 20% amorphous water suspending agent of the compound A is thermally stored for 14 days, the product is obvious in water evolution, the fluidity is poor, and the preparation property is obviously inferior to that of the 20% crystalline water suspending agent of the compound A.
According to the heat storage experimental results, the compound A crystal form I water suspending agent has excellent heat storage stability, the water separation rate of the suspending agent product is less than 5% after 14 days of heat storage, the suspension rate is more than 99%, the particle size of the suspending agent product is not obviously changed, and the fluidity of the preparation is good.
EXAMPLE 4 stability test of form I
About 2-3 mg of the crystal form I (initial purity 99.07%) obtained in example 1 is weighed, placed in an oven at 80 ℃ in a closed state, sampled and measured for XRPD and HPLC after 1 day, placed in a stabilizing box at 25 ℃ per 60% RH, 40 ℃ per 75% RH, and sampled and measured for XRPD and HPLC after 1 week.
The experimental results are shown in Table 9, and the results show that the crystal form I is not obviously changed in crystal form and purity after being placed under the conditions of 25 ℃ and 60% RH and 40 ℃ and 75% RH, the crystal form is not obviously changed after being placed under the condition of 80 ℃ and the purity is slightly reduced.
The crystal form I has good physical/chemical stability under the conditions of 25 ℃ to 60% RH and 40 ℃ to 75% RH, can be kept stable without specific temperature and humidity control conditions in the storage and use process, and can well meet the requirements of medicine storage and use.
Table 9 results of Compound A form I thermal stability experiments
* Relative purity = test sample HPLC purity/starting sample HPLC purity x 100%
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.

Claims (11)

1. A crystalline form i of methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate, characterized by a diffraction angle 2Θ in an X-ray diffraction pattern under Cu-Ka radiation having a characteristic peak at 12.0 ° ± 0.2 °,13.4 ° ± 0.2 °,24.8 ° ± 0.2 °.
2. Form i according to claim 1, characterized in that in the X-ray diffraction pattern under Cu-Ka radiation, the diffraction angle 2Θ has a characteristic peak at 12.0 ° ± 0.2 °,13.4 ° ± 0.2 °,24.8 ° ± 0.2 °,18.2 ° ± 0.2 °,19.1 ° ± 0.2 °,23.3 ° ± 0.2 °,20.1 ° ± 0.2 °,22.2 ° ± 0.2 °,29.2 ° ± 0.2 °.
3. Form i of claim 1, wherein the diffraction angle 2Θ has a characteristic peak at 10.9±0.2°,12.0±0.2°,13.4±0.2°,18.2±0.2°,18.6±0.2°,19.1±0.2°,19.6±0.2°,20.1±0.2°,20.8±0.2°,21.1±0.2°,22.2±0.2°,23.3±0.2°,24.0±0.2°,24.2±0.2°,24.8±0.2°,25.2±0.2°,26.1±0.2°,26.6±0.2°,26.9±0.2°,27.6±0.2°,29.2±0.2°,30.1±0.2°,32.1±0.2°,34.1±0.2°,36.5±0.2°,39.6±0.2° in the X-ray diffraction pattern of Cu-Ka radiation.
4. Form i of claim 1, wherein form i has an X-ray powder diffraction pattern substantially as shown in figure 1.
5. A process for the preparation of the crystalline form i according to any one of claims 1 to 4, comprising the steps of:
(1) Under heating, amorphous methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate is dissolved in a single solvent or a mixed solvent;
(2) Precipitating the dissolved methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate as a solid under reduced temperature;
(3) Separating the precipitate to obtain the crystal form I of the methyl 2- [ [ [ 4-chloro-2-fluoro-5- [ (2, 2-trifluoroethyl) thio ] phenyl ] amino ] methyl ] benzoate.
6. The method of claim 5, wherein the solvent is selected from at least one of petroleum ether, methanol, ethanol, isopropanol, propanol, butanol, ethylene glycol, 1, 2-propanediol, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, ethyl acetate, toluene, xylene, acetonitrile, tetrahydrofuran, dioxane, methyl t-butyl ether, acetone, methyl isobutyl ketone, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, or water.
7. An insecticidal and acaricidal composition comprising the crystalline form i according to any one of claims 1 to 4, wherein the crystalline form i comprises 1% to 50% by weight.
8. The insecticidal and acaricidal composition according to claim 7, further comprising a component B, wherein the weight percentage of the component B is 1% -50%.
9. The insecticidal and acaricidal composition according to claim 8 wherein component B is selected from the group consisting of: isoprocarb, carbosulfan, benfuracarb, carbosulfan, methomyl fenobucarb, methomyl, propoxur, fenoxycarb, oxadiazon carbaryl, furacarb, pirimicarb, carbofuran, aldicarb, carbofuran, carbosulfone, carbofuran, thiodicarb, monocrotophos carbosulfan, methiocarb, mixed carbofuran, methomyl the preparation process includes the steps of chlorpyrifos, dimchip, dichlorvos, isoxacarb, pyrimidyl the composition comprises the components of benomyl, dimchip, chlorpyrifos isoxacarb, pyrimidyl, Chlorpyrifos, chlorpyrifos methyl, triazophos phoxim, profenofos chlorpyrifos, chlorpyrifos methyl, triazophos, phoxim, profenofos, chlorpyrifos thiophos, methidathion, fenitrothion, malathion, valinate diazinon, fenthion, pyrazophos, pyridazinethion, iminothion, quetiaphos, acephate, isosalazine, oxazolphos, pyrazophos, butyl pyrimidos, phenthoate, fenitrothion, terbutafos, aphos, dimethoate, omethoate, dicamba, phosphamide, dibromo, fast-acting, trichlorfon, dichlorvos, Fenpropaphos, chlorfenphos, fenphos, baizhfos, methylphos, profenofos, sulfoxyphos, heptenophos, napeptidos, housefly phosphorus, coumaphos, ethion, methamphhos, phoxim, chlorzophos, yigossyphos, bap, valvap, cartap, mevalonate, phoxim, dithiophos, parathion, methylparathion, methamidophos, benfofos, nitenfos, dichlorphos, bap, monocrotophos, tebufos, carprofen, fenphos, ethyl ester phosphorus, cloxyphos, chlormefos, tian Le phosphorus, monothio Tian Le phosphorus, dithio Tian Le phosphorus, inner phosphorus, methyl inner phosphorus, sulfone phosphorus, feng Bing phosphorus, isozone, chlorpyrifos, methyl ethyl ester phosphorus, chlorpyrifos, isosulfate phosphorus, sulfenphos, cyfos, benfofos, amifos, triazophos phosphorus, su Liu phosphorus, phoxim, methyl piroxicam phosphorus-emitting, su Liu phosphorus, lipoylthiophosphate methyl phoxim, methyl piroxicam bupirifos, li Lifu S, pyrimidephosphine, methylpyrimidin, fosthiazate, bromthion, ethylbromthion, trithion, chlorpyrifos, borer-killing eye, animal tick phosphorus Isoprophos, desmopraph, cyromazine, fenitrothion, thiophos-iodide, phoxim sulfoxide, fenthion, butyl phosphine, tetramethylphosphorus, dinotefuran, phoxim, chlorpyrifos, Pogostemon, benzonitrile phosphine, bromophenylphosphine, fenphospine, buthion, dinotefuran, thiocyclophos, methylthiocyclophosphane, chloramine phosphorus, aqueous amine phosphorus, methylisophos, glycifos, meflofos, prilofloxacin, octamethylphos, triphostin, bromophenon, azido, methamidophos, ethiona, azophos, O- {2- [ acetyl (ethyl) amino ] -6-methyl-4-pyrimidinyl } O, O-diethyl thiophosphate, pyrimidos, mequinos, ethylmethiphos, p-chlorphos, le Naisong-3, triavone, quinalphone, thiopyranos, thiosaliphos, methylisophos, amine phosphorus, termidothiophos, endophos-O, chlormezophos, Phosphopiride, oxford propyl thiophos, ethyl thiophos, benoxaphos, cypermethrin high-efficiency cyhalothrin, fenpropathrin, fenvalerate, fen high-efficiency cyhalothrin, fenpropathrin fenvalerate, fenvalerate cyhalothrin, permethrin, cyfluthrin, allethrin, bioallethrin beta-cypermethrin, beta-cypermethrin beta-cypermethrin, beta-cypermethrin high-efficiency trans-cypermethrin, Propathrin, phenothrin, bifenthrin, biotinylethrin, cis-bifenthrin, bifenthrin and tefluthrin, tetramethrin, tefluthrin, tetrabromothrin tefluthrin, tetramethrin, tefluthrin tefluthrin, tetrabromothrin Cyantraniliprole, cyhalothrin, permethrin, d-trans-permethrin, fenpropathrin, fenpicrin, fenpic penflufen, cyhalothrin, S-fenvalerate, bifenthrin, fenpropathrin penflufen, cyhalothrin, fenfluramine, fenvalerate, fenvaler S-fenvalerate, bifenthrin, N-cyhalothrin, Deltamethrin, tethrin, trifluorethrin, fenacet, fentanyl propionate flusilathrinate, thiooxime ether, thiofluorooxime ether, flumethrin, chamomile, fenpyrad silafluofen, thiooxime ether, thiofluorooxime ether flumethrin, smoked worm chrysanthemum acetamiprid, dinotefuran, clothianidin, nitenpyram, thiacloprid, imidaclothiz, flonicamid, piprolin, sulfluramid, flupirofuranone, trifluoperazine, chlorpyrifos, chlorfenapyr fipronil, abamectin, emamectin benzoate, abamectin lepidomycin, milbemycin, nitenpyram, methoprene, dipivoxil, and is also available in the form, The composition comprises methoprene, pyriproxyfen, clofentezine, flufenzine, hexythiazox, etoxazole, matrine, azadirachtin, bacillus thuringiensis, beauveria bassiana, allicin, neonicotinoid, carvacrol, d-limonene, nicotine, protonicotin, oxymatrine, pyrethrin, guathrin I, gualasin II, heliothin I, heliothin II, pyrethrin I, pyrethrin II, matrine, azalide-III, rotenone, rypsin, resveratrol, bacillus sphaericus, sanguinarine, triptolide, diafenthiuron, azocyclotin, tricyclin, fenbutatin, propargite, chlorfenapyr, dinitril, flubendiamide, sulfenuron, cartap, thiocyclam, dimehypo, diflubenzuron, lufenuron, hexaflumuron chlorbenzuron, triflumuron, flufenoxuron, polyfluorocarbazide, novaluron chlorbenzuron, triflumuron, flufenoxuron flucycloxuron, polyfluorocarbazide, fluoroureide Furformyl hydrazine, chlorantraniliprole, methoxyfenozide, tebufenozide, antifeedant hydrazine, chromafenozide, alpha ecdysone, ecdysterone, benomyl, precocity I precocin II, juvenile hormone I, juvenile hormone II, juvenile hormone III, triazophos, chlorfenapyr, pyriminostrobin, bifenazate, fenpyroximate, Pyriminostrobin, tebufenpyrad, pyridaben, tolfenpyrad, indoxacarb, metaflumizone spirodiclofen, spiromesifen, spirotetramat, spirodiclofen, methoxypiperidine ethyl spirodiclofen, spiromesifen, spirotetramat, and the like spirodiclofen, methoxypiperidine ethyl ester flucyantraniliprole, tetrazole-carboxamide, chlorflubendiamide, fluxapyroxad-amide the composition comprises the components of clothianidin, pymetrozine, chlorfenapyr, dicycloprid, alopecuroide, chlorfenapyr, chlorfena chlorpyrifos, copper naphthenate, clomiphene, dixanthogen, fenbuconazole, fenoxacin, fluoroquin, metaflumizone, tebufenozide, flumetsulam, triclosan, chlorfenapyr, Trifluomethyl, fluazifop-methyl, lei Fusha-naphthalene, thuringiensis, fenpyroximate, triadimefon, bromoacetamide, copper sulfate, ferric phosphate, metaldehyde, molluscacide, sodium pentachlorophenate, pyrrocarbonitrile, tributyltin oxide, molluscacide, nitropropofol, pentanifhol, oxadiazon, azomethine, buprofezin, chlorpyrifos, fluurea, sulfofuron, maltodextrin, boric acid, diatomaceous earth, silica gel, triazene, borax, lime, copper oleate, mercuric chloride, potassium thiocyanate, sodium thiocyanate, chlordane, thiodane, ethiprole, fipronil, spinosad, spinetoram, praziquantel, difenoconazole, flufenacet, isoxaben, Fluoropyrimidine, ring Ding Fulun, oxazolothioyl, thiabendazole, benzopyran, or dichlorothiazole.
10. An insecticidal and acaricidal composition according to claim 7 wherein the dosage form of the insecticidal and acaricidal composition is selected from the group consisting of suspending agents, soluble granules, seed-dressing agents, granules, microparticles and water dispersible granules.
11. Use of a crystalline form i according to any one of claims 1 to 4 and/or a pesticidal and acaricidal composition according to any one of claims 7 to 10 for controlling insect pests, acari.
CN202310517154.7A 2023-05-09 2023-05-09 A new crystal form of trifluoroethyl sulfide compound, preparation method thereof, insecticide and acaricide composition and application thereof Pending CN118930463A (en)

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