WO2019010718A1 - Forme cristalline b de dicarfentrazone-éthyle, son procédé de préparation et son utilisation - Google Patents

Forme cristalline b de dicarfentrazone-éthyle, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2019010718A1
WO2019010718A1 PCT/CN2017/093068 CN2017093068W WO2019010718A1 WO 2019010718 A1 WO2019010718 A1 WO 2019010718A1 CN 2017093068 W CN2017093068 W CN 2017093068W WO 2019010718 A1 WO2019010718 A1 WO 2019010718A1
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WIPO (PCT)
Prior art keywords
oxazolone
crystal
acid
crystal form
ester
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PCT/CN2017/093068
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English (en)
Chinese (zh)
Inventor
赵德
金涛
宋伟
张兆真
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青岛清原化合物有限公司
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Publication of WO2019010718A1 publication Critical patent/WO2019010718A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Definitions

  • the invention belongs to the technical field of herbicide crystallization process, and particularly relates to a crystal form of oxazolone B, a preparation method thereof and use thereof.
  • the oxazolone is a newly developed HPPD inhibitor herbicide for post-emergence stem and leaf treatment of wheat field. It has excellent biological activity and can effectively control a variety of malignant weeds in wheat fields.
  • the compound patent has been authorized.
  • the polymorphism phenomenon refers to a phenomenon in which solid materials are arranged in two or more different spatial arrangements to form solid states having different physicochemical properties.
  • polymorphs include multi-component crystalline forms such as organic solvates, hydrates, and the like.
  • Drug polymorphism is widespread in drug development and is an inherent property of organic small molecule compounds. In theory, small molecule drugs can have an infinite number of crystal packing methods - polymorphs.
  • Polymorphism is not only controlled by the internal structure of the molecule itself, functional group properties, intramolecular and intermolecular interactions, but also by drug synthesis process design, crystallization and purification conditions, formulation excipient selection, formulation process Route and granulation methods, as well as storage conditions, packaging materials and other factors. Different crystal forms have different colors, melting points, dissolution, dissolution properties, chemical stability, reactivity, mechanical stability, etc. These physical and chemical properties or processability sometimes directly affect the safe and effective performance of the drug. Therefore, crystal research and control has become an important research content in the drug development process.
  • the invention provides a novel herbicide oxazolone B crystal form, a preparation method thereof and a use thereof, and the oxazolone B crystal form has good stability and good control effect on weeds, and can be used for controlling weeds in the wheat field after seedlings.
  • oxadiazepine is prepared by the method of CN 105503728 B.
  • 2.5 g (0.022 mol) of 1,3-dimethyl-5-hydroxypyrazole and 30 mL of toluene were placed in a three-necked flask, and 9.0 g of triethylamine (0.09 mol) was added with stirring.
  • the temperature of the ice bath is controlled at 5-10 ° C, and a solution of 6.3 g (0.022 mol) of 2-methanesulfonyl-4-trifluoromethylbenzoyl chloride is added dropwise to control the reaction temperature to not exceed 15 ° C. The addition is completed and removed.
  • Examples 6 to 60 referring to the synthesis methods of Examples 1 to 5, the reaction product was replaced with the corresponding pyrazole compound and the corresponding acid chloride or halogenated product to obtain a reaction number of 006 as shown in Table 1.
  • Test data for each of the compounds numbered 006 to 060 are listed in Table 1.
  • the oxazolone described in the present application is the compound described in Example 21.
  • the prepared drug of oxazolone is a crystal form of A, and on the basis of the crystal form of A, the crystal form of B is further studied.
  • I/I 0 values are 81.1, 41.7, 30.5, 37.1, 6.5, 18.5, 42.6, 10.8, 29.9, 25.2, 46.6, 16, 74.4, 31.3, 36.7, 100, 43, 21.6, 14.5, 9.1, 29.9, respectively. , 15.2, 31.7, 12.4, 14.8.
  • its X-ray powder diffraction pattern is substantially as shown in FIG.
  • the preparation method of the oxazolone B crystal form comprises the steps of dissolving oxazolone in methanol, ethyl acetate, isopropyl acetate, 1,4-dioxane or butanone, and heating to complete After dissolution, it naturally volatilizes until the solvent is completely evaporated, and the obtained crystal is B crystal.
  • the oxazolone is dissolved in a mixed solution of n-butanol and isobutanol, heated to 55 ° C, and then cooled to 0 to 5 ° C to be allowed to stand for crystallization, filtered, and the crystal obtained after drying is a B crystal form.
  • a herbicidal formulation comprising the oxazolone B crystal form and an adjuvant.
  • the adjuvant is selected from one or more of the group consisting of a solvent, a solid diluent, an emulsifier, a wetting agent, a dispersing agent, an antifreezing agent, an antifoaming agent, and a thickening agent.
  • Selected solvents include, but are not limited to, polar solvents: water, N, N-dimethyl amide, dimethyl sulfoxide, N-alkyl pyrrolidone, methanol, ethanol, ethylene glycol, isopropanol, ethylene glycol Butyl ether, propylene glycol methyl ether, etc.; aromatic hydrocarbon solvent oil series: toluene, xylene, solvent oil No. 100, solvent oil No. 150, solvent oil No. 180, solvent oil No.
  • vegetable oils castor oil, linseed oil, sesame oil , corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and their corresponding methylated vegetable oils
  • ketones cyclopentanone, cyclohexanone, cyclooctanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone and the like
  • acetates methyl acetate, ethyl acetate, propyl acetate, sec-butyl acetate, isoamyl acetate, hexyl acetate, heptyl acetate and acetic acid Octyl ester, etc.
  • other classes such as phthalamide, cyclohexanol, decyl alcohol, benzyl alcohol and tetrahydrofurfuryl alcohol.
  • the solid diluent selected may be water soluble or water insoluble.
  • Water-soluble solid diluents include, but are not limited to, salts such as alkali metal phosphates (sodium dihydrogen phosphate), alkaline earth metal phosphates, sodium, potassium, magnesium and zinc sulfates, sodium chloride and potassium chloride, sodium acetate Sodium carbonate and sodium benzoate, and sugars and sugar derivatives such as sorbitol, lactose, sucrose and mannitol, corn starch and the like.
  • Examples of water-insoluble solid diluents include, but are not limited to, clay, calcium carbonate, diatomaceous earth, silica, calcium silicate, bentonite, magnesium aluminum silicate, kaolin, and the like.
  • Wetting agents include, but are not limited to, alkyl sulfosuccinates, laurates, alkyl sulfates, phosphates, ethoxylated alcohols, ethoxylated silicones, alkylphenol ethoxylates , benzenesulfonate, alkyl-substituted benzenesulfonate, alkyl alpha-olefin sulfonate, naphthalenesulfonate, alkyl-substituted naphthalenesulfonic acid alkali metal salt, naphthalenesulfonic acid alkali metal salt and alkyl substitution a condensate of naphthalene sulfonate and formaldehyde, an ethoxylate of an alcohol.
  • Dispersing agents include, but are not limited to, sodium, calcium and ammonium salts of lignosulfonic acid; sodium and ammonium salts of maleic anhydride copolymers; sodium salts of condensed phenolsulfonic acid; naphthalenesulfonate-formaldehyde condensates a phosphate ester dispersant, a polycarboxylate dispersant, and the like.
  • Thickeners include, but are not limited to, guar gum, pectin, xanthan gum, alginate, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose.
  • Synthetic thickeners include derivatives of the foregoing classes, and also include polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, various polyethers and copolymers thereof, and polyacrylic acid and salts thereof.
  • formulation ingredients such as dyes, antifoaming agents, desiccants, and the like can be used in the present invention. These ingredients are well known to those skilled in the art.
  • the composition also includes other active ingredients.
  • Suitable active ingredients which can be mixed with the crystalline form of the oxazolone B of the present invention are, for example, "World Pesticide New Variety Technology Encyclopedia", China Agricultural Science and Technology Press, 2010.9 and known materials in the literature cited herein.
  • the various substances mentioned below (remarks: the name of the compound, or the common name according to the International Organization for Standardization (ISO), or the chemical name, when appropriate): acetochlor, butachlor, thyroxine Amine, propisochlor, metolachlor, stilbenamide, pretilachlor, chlorfenapyr, acetochlor, naproxil, R-L-naproxil, diazepam, benzene Thiacil, dibenzoylamine, flufenacetate, herbicide, flufenic acid, bromobutyramide, dimethoprim, high-performance metolachlor, acetophenone Amine, flufenacet, methoxymethafen, metazachlor, iso
  • the other active ingredients include, but are not limited to, sodium 2-methyltetrachloride, 2-methylisochlorooctyl ester, 2,4-D butyl ester, 2,4-D isooctyl ester, and 2 methyl 4-chloroformate.
  • Amine salt flufenoxyacetic acid, isooctyl chlorofluoxetine, fluorochloropyridinium, dicamba, isoproturon, chloromeron, piracetamide, flufenyl, oxazolone, Diflufenazone, fenoxapropion, clodinafop (acid), oxadiazon, oxazolin, chlorpyrifos, methyl disulfuron, flucarbazone, difluorosulfonate Amine, acesulfame, oxazinone, chlorpyrifos, tertidine, bentazone, bromoxynil, octanoyl bromoxynil and flufenacet.
  • the total mass content of the active ingredient in the composition is within 75%, preferably within 50%.
  • the dosage form of the composition is an aqueous suspension (SC), a dispersible oil suspension (OD), an emulsifiable concentrate (EC), a microemulsion (ME), a granule (GR), a suspoemulsion (SE) or a water-dispersible granule. (WDG).
  • SC aqueous suspension
  • OD dispersible oil suspension
  • EC emulsifiable concentrate
  • ME microemulsion
  • ME microemulsion
  • GR granule
  • SE suspoemulsion
  • WDG water-dispersible granule.
  • oxazolone B crystal form or the herbicidal compounding composition for controlling broadleaf weeds and some grass weeds in a wheat field.
  • the crystal form of the oxazolone B of the invention has good stability, and the compound composition of the B crystal form or other active ingredients has good control effects on broad-leaved weeds and some grass weeds in the wheat field, The effect is significantly better than the A crystal form.
  • Figure 1 is an XRPD pattern of the crystalline form of the oxazolone A of Example 1 of the present invention.
  • Figure 2 is an XRPD pattern of the crystalline form of the oxazolone B of Example 2-3 of the present invention.
  • Instrument model Bruker D8advance, target: Cu K ⁇ (40kV, 40mA), sample to detector distance: 30cm, scanning range: 3 0 - 45 0 (2 ⁇ value), scanning step: 0.05s.
  • the crude drug of oxazolone was prepared according to the method of CN 105503728 B, and it was a crystal form of A.
  • oxazolone A crystal form was placed in a 10 L flask, and methanol, ethyl acetate, isopropyl acetate, 1,4-dioxane or butanone 6 L was added, and the mixture was stirred while heating until the starting material was completely dissolved. Thereafter, it is naturally volatilized at 25 ° C until the methanol is completely evaporated to obtain a oxazolone B crystal powder.

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

Abstract

La présente invention concerne le domaine technique des procédés de cristallisation d'herbicides, et concerne en particulier une forme cristalline B de dicarfentrazone-éthyle, son procédé de préparation et son utilisation. Le diagramme de diffraction de rayons X sur poudres de la forme cristalline B de dicarfentrazone-éthyle présente des pics caractéristiques à des angles de diffraction 2θ de 7,998, 11,539, 13,821, 15, 15,742, 16,158, 17,161, 17,781, 18,177, 19,02, 20,241, 20,52, 21,419, 21,797, 22,421, 24,018, 24,278, 26,262, 26,579, 26,982, 28,121, 29,88, 30,26, 34,157 et 38,14, la plage d'erreur 2θ étant de ± 0,2°. La forme cristalline B de dicarfentrazone-éthyle présente une bonne stabilité, et présente un meilleur effet de lutte contre les mauvaises herbes à larges feuilles et certaines mauvaises herbes graminées lorsqu'elle est présente dans une composition de composé avec d'autres ingrédients efficaces, l'effet étant significativement meilleur que celui de la forme cristalline A.
PCT/CN2017/093068 2017-07-13 2017-07-15 Forme cristalline b de dicarfentrazone-éthyle, son procédé de préparation et son utilisation WO2019010718A1 (fr)

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CN201710567969.0A CN107311930B (zh) 2017-07-13 2017-07-13 双唑草酮b晶型及其制备方法和用途
CN201710567969.0 2017-07-13

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CN107897191B (zh) * 2017-11-09 2021-11-30 青岛清原化合物有限公司 一种含苯唑氟草酮的除草组合物及其应用
CN113016811A (zh) * 2017-11-09 2021-06-25 青岛清原化合物有限公司 一种含双唑草酮的除草组合物及其应用
CN109601548A (zh) * 2019-01-25 2019-04-12 河北省农林科学院粮油作物研究所 一种防治小麦田阔叶杂草和禾本科杂草除草剂组合物
CN113117559A (zh) * 2021-04-20 2021-07-16 安徽省圣丹生物化工有限公司 一种除草剂制备用复配釜及其使用方法

Citations (3)

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CN103980202A (zh) * 2014-05-27 2014-08-13 青岛清原化合物有限公司 一种具有除草活性的4-苯甲酰吡唑类化合物
CN105230629A (zh) * 2015-11-17 2016-01-13 青岛清原抗性杂草防治有限公司 增效除草组合物
CN105503728A (zh) * 2015-12-31 2016-04-20 青岛清原化合物有限公司 吡唑类化合物或其盐、制备方法、除草剂组合物及用途

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CN105685049B (zh) * 2016-03-15 2017-12-22 青岛清原化合物有限公司 一种高粱田除草组合物及其应用
CN106070309B (zh) * 2016-06-21 2018-06-15 江苏清原农冠抗性杂草防治有限公司 含有双唑草酮的复配除草组合物及其使用方法
CN106305754A (zh) * 2016-10-13 2017-01-11 广东中迅农科股份有限公司 含有双唑草酮和二氯喹啉酸以及氯吡嘧磺隆的除草组合物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103980202A (zh) * 2014-05-27 2014-08-13 青岛清原化合物有限公司 一种具有除草活性的4-苯甲酰吡唑类化合物
CN105230629A (zh) * 2015-11-17 2016-01-13 青岛清原抗性杂草防治有限公司 增效除草组合物
CN105503728A (zh) * 2015-12-31 2016-04-20 青岛清原化合物有限公司 吡唑类化合物或其盐、制备方法、除草剂组合物及用途

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