WO2018201523A1 - 无定形态苯唑氟草酮及其制备方法和用途 - Google Patents

无定形态苯唑氟草酮及其制备方法和用途 Download PDF

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WO2018201523A1
WO2018201523A1 PCT/CN2017/084905 CN2017084905W WO2018201523A1 WO 2018201523 A1 WO2018201523 A1 WO 2018201523A1 CN 2017084905 W CN2017084905 W CN 2017084905W WO 2018201523 A1 WO2018201523 A1 WO 2018201523A1
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oxazolone
amorphous
herbicidal
fluridone
oxacillin
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PCT/CN2017/084905
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English (en)
French (fr)
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赵德
张兆真
宋伟
彭学岗
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青岛清原化合物有限公司
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Publication of WO2018201523A1 publication Critical patent/WO2018201523A1/zh

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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
    • 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

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  • the invention belongs to the technical field of herbicide crystallization process, and particularly relates to an amorphous form of oxazolone and its preparation method and use.
  • Oxazolone is a newly developed HPPD inhibitor herbicide for post-emergence stem and leaf treatment of corn fields. It has excellent biological activity and can effectively control a variety of malignant weeds in corn fields. Compound patents have been authorized, and the authorization number is: CN 105503728 B.
  • the amorphous form is a form of polymorphism in matter and a special crystalline state.
  • the amorphous form is one of a plurality of crystalline forms, and the various physical and chemical properties and effects of the amorphous drug are generally different from those of the general crystalline form. Therefore, in the polymorphic study of solid drugs, the in-depth discussion of amorphous substances has important scientific significance. However, since the amorphous form is a thermodynamic instability system, crystal transformation is extremely prone to occur, which is also the most important obstacle to the problem of amorphous drugs.
  • the invention provides a novel herbicide amorphous form of oxazolone and its preparation method and use.
  • the amorphous form of oxazolone has no sharp diffraction peak on the X-ray powder diffraction pattern, has good stability, high solubility in water, good control effect on weeds, and can be used for controlling weeds after corn seedlings.
  • oxazolone is prepared by the method of CN 105503728 B.
  • Prepared benzoazole fluoride The original drug of oxaloacetone is Form A, and the original drug of oxazolone is dissolved in a series of solvents: methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, acetonitrile, tetrahydrofuran, nitromethane, ethyl acetate, acetic acid.
  • the X-ray powder diffraction pattern is substantially as shown in FIG.
  • the preparation method of the amorphous form of oxazolone comprises the following steps: stirring oxafluridone in dichloromethane, and evaporating the solvent under reduced pressure at 40-60 ° C, preferably at a temperature of 45-50 ° C. After mechanical grinding, an amorphous form is obtained.
  • a herbicidal composition comprising the amorphous form of oxazolone active ingredient and an adjuvant.
  • the auxiliary agent is selected from one or more 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 amorphous form of the oxazolone 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, is
  • the other active ingredients include, but are not limited to, atrazine, terbutin, octanoyl bromoxynil, nicosulfuron, chlorsulfuron, flupiroxine, dicamba, acetochlor One or more of butachlor, bentazone, diflufenic acid, oxazolone, methyl oxazinate, 2 methyl 4-chloro and oxazinone.
  • the total mass content of the active ingredients in the composition is within 75%, preferably within 50%.
  • the dosage form of the composition is a suspending agent (SC), a dispersible oil suspending agent (OD), an emulsifiable concentrate (EC), a microemulsion (ME), a granule (GR), a suspoemulsion (SE) or a water-dispersible granule ( WDG).
  • SC suspending agent
  • OD dispersible oil suspending agent
  • EC emulsifiable concentrate
  • ME microemulsion
  • ME microemulsion
  • GR granule
  • SE suspoemulsion
  • WDG water-dispersible granule
  • the amorphous form of the oxazolone of the invention Compared with the A crystal form, the amorphous form of the oxazolone of the invention has good physical and chemical stability, and does not undergo crystal transformation within two months after storage at a high temperature of 55 ° C, and the purity is not substantially reduced, and the solubility in water is increased by one.
  • the amorphous form of oxafluridone and the compound composition with other active ingredients have very good control effects on corn field weeds and some broad-leaved weeds, and have a good application prospect.
  • Figure 1 is an XRPD pattern of the crystalline form of the oxazolone A of Example 1 in the present invention.
  • Figure 2 is an XRPD pattern of the crystalline form of the amorphous form of oxazolone in Example 2 of the present invention.
  • Instrument model Bruker D8advance, target: Cu K ⁇ (40kV, 40mA), sample to detector distance: 30cm, scanning range: 3°-40° (2 ⁇ value), scanning step: 0.05s.
  • the original drug of oxazolone was prepared according to the method of CN 105503728 B. Then add 3000 g of oxazolone to a 10 L flask, add 5 L of ethyl acetate, heat to 50 ° C, stir until the starting material is completely dissolved, cool to 0 ° C, let stand for 2 hours, filter, 30 ° C often The mixture was dried by bubbling air for 5 hours to obtain a powder of the crystalline form of oxazolone A. Alternatively, the solvent may be volatilized until the solvent has completely evaporated, and a powder of the crystalline form of the oxazolone A can also be obtained.
  • Example 1 The crystalline form of the oxazolone A obtained in Example 1 and the amorphous form of oxazolone obtained in Example 2 were subjected to HPLC analysis, and the A crystal form and the amorphous form were both 95.0%.
  • the two powders were placed in an oven at 25 ° C, 35 ° C, 45 ° C and 55 ° C for 2 months for heat storage experiments, after which the crystal type and purity were tested. The results are shown in Table 1 below:
  • Example 2 The crystalline form of the oxazolone A obtained in Example 1 and the amorphous form of oxazolone obtained in Example 2 were dissolved in pure water and shaken at 25 ° C for 24 hours to fully dissolve. After that, it is filtered with filter paper, and the filtrate is filtered through 0.22 ⁇ m. After the membrane and mobile phase were dissolved, the solubility in water was determined by HPLC. The results are shown in Table 2 below:
  • Example 2 amorphous form of oxazolone 6.6
  • Example 1 oxazolone A crystal form 3.2

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Abstract

提供一种无定形态苯唑氟草酮及其制备方法、除草组合物和用途。该无定形态苯唑氟草酮的X射线粉末衍射谱图上没有尖锐的衍射峰，优选地，其X射线粉末衍射图谱基本上如图2所示。该无定形态苯唑氟草酮与苯唑氟草酮A晶型相比，物理化学稳定性好，在55℃高温下储存两个月未发生晶型转变，纯度也基本未降低，同时水中溶解度增加一倍。无定形态苯唑氟草酮的除草组合物及其与其它有效成分的复配除草组合物对玉米田禾本科杂草及部分阔叶杂草均有较好防除效果，具有良好应用前景。

Description

无定形态苯唑氟草酮及其制备方法和用途 技术领域
本发明属于除草剂结晶工艺技术领域，具体涉及到一种无定形态苯唑氟草酮及其制备方法和用途。
背景技术
苯唑氟草酮的化学名称：4-(2-氯-4-(甲磺酰基)-3-((2,2,2-三氟乙氧基)甲基)苯甲酰基)-1-乙基-1H-吡唑-5-基-1,3-二甲基-1H-吡唑-4-甲酸酯
结构式：
Figure PCTCN2017084905-appb-000001
苯唑氟草酮是新研发的玉米田苗后茎叶处理的HPPD抑制剂类除草剂，具有优异的生物活性，可以有效防除玉米田多种恶性杂草，化合物专利已被授权，授权公告号：CN 105503728 B。
无定形态是物质存在多晶型现象的一种形式，也是一种特殊的晶型状态。对于具有多晶型现象的固体药物，无定形态是其多种晶型状态中的一种，无定形态药物的各种理化性质及药效通常有别于一般的晶型药物。因此，在固体药物的多晶型研究中，对无定形态物质的深入探讨有重要科学意义。但由于无定形态为热力学不稳定性体系，极容易发生晶型转变，这也是困扰无定形态药物的最主要障碍。
由于苯唑氟草酮为最新研制的药物，目前各种文献及专利中均没有其晶型的报道，且经研究发现大多数情况下，苯唑氟草酮都以A晶型存在。
发明内容
本发明提供了一种新型除草剂无定形态苯唑氟草酮及其制备方法和用途。所述无定形态苯唑氟草酮在X-射线粉末衍射图谱上没有尖锐的衍射峰，稳定性好，水中溶解度高，对杂草防治效果好，可用于玉米田苗后防除杂草。
本发明的技术方案，苯唑氟草酮参照CN 105503728 B中的方法制备。制备得到的苯唑氟 草酮原药为A晶型，同时将苯唑氟草酮原药溶解在系列溶剂中：甲醇、乙醇、异丙醇、丙酮、丁酮、乙腈、四氢呋喃、硝基甲烷、乙酸乙酯、乙酸异丙酯、异戊醇、甲基叔丁醚、甲苯、甲基异丁基甲酮、正己烷、正庚烷、乙醚、氯仿、石油醚或水等等，加热搅拌至完全溶解，降温静置结晶或缓慢挥发，干燥，均得到A晶型。
在A晶型的基础上，又研究了苯唑氟草酮的无定形态。
一种无定形态苯唑氟草酮，经X-射线粉末衍射检测是以无定型的形式存在的。
其X-射线粉末衍射图谱上没有尖锐的衍射峰，优选地，其X射线粉末衍射图谱基本上如图2所示。
所述无定形态苯唑氟草酮的制备方法，包括以下步骤：将苯唑氟草酮搅拌溶解在二氯甲烷中，于40-60℃减压旋转蒸发溶剂，优选温度为45-50℃，之后经机械研磨，得到无定形态。
一种除草复配组合物，包括所述的无定形态苯唑氟草酮有效成分和助剂。
所述助剂选自溶剂、固体稀释剂、乳化剂、润湿剂、分散剂、防冻剂、消泡剂和增稠剂中的一种或多种。
所选溶剂包括但不限于极性溶剂类：水、N,N-二甲基酰胺、二甲基亚砜、N-烷基吡咯烷酮、甲醇、乙醇、乙二醇、异丙醇、乙二醇丁醚、丙二醇甲醚等；芳烃溶剂油系列：甲苯、二甲苯、100号溶剂油、150号溶剂油、180号溶剂油、200号溶剂油等；植物油类：蓖麻油、亚麻籽油、芝麻油、玉米油、花生油、棉籽油、大豆油、菜籽油以及它们对应的甲酯化植物油等；酮类：环戊酮、环己酮、环辛酮、2-庚酮、异佛尔酮和4-羟基-4-甲基-2-戊酮等；乙酸酯类：乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸仲丁酯、乙酸异戊酯、乙酸己酯、乙酸庚酯和乙酸辛酯等；其余类如：癸酰胺、环己醇、癸醇、苯甲醇和四氢糠醇等。
所选固体稀释剂可以是水溶性或非水溶性的。水溶性固体稀释剂包括但不限于：盐，例如碱金属磷酸盐(磷酸二氢钠)、碱土金属磷酸盐、钠、钾、镁和锌的硫酸盐、氯化钠和氯化钾、乙酸钠、碳酸钠和苯甲酸钠、以及糖和糖衍生物，例如山梨糖醇、乳糖、蔗糖和甘露醇、玉米淀粉等。非水溶性固体稀释剂的例子包括但不限于：粘土、碳酸钙、硅藻土、白炭黑、硅酸钙、膨润土、硅酸镁铝和高岭土等。
润湿剂包括但不限于：烷基磺基琥珀酸盐、月桂酸盐、烷基硫酸盐、磷酸酯、乙氧基氟化醇、乙氧基化的硅酮、烷基苯酚乙氧基化物、苯磺酸盐、烷基取代的苯磺酸盐、烷基α-烯烃磺酸盐、萘磺酸盐、烷基取代的萘磺酸碱金属盐、萘磺酸碱金属盐和烷基取代的萘磺酸酯与甲醛的缩合物、醇的乙氧基化物。
分散剂包括但不限于：木质素磺酸的钠盐、钙盐和铵盐；马来酸酐共聚物的钠盐和铵盐；缩合的苯酚磺酸的钠盐；萘磺酸酯-甲醛缩合物；磷酸酯类分散剂、聚羧酸盐类分散剂等。
增稠剂包括但不限于：瓜尔胶、果胶、黄原胶、藻酸盐、甲基纤维素、羟乙基纤维素、羟丙基纤维素和羧甲基纤维素。合成的增稠剂包括前述种类的衍生物，还包括聚乙烯醇、聚丙烯酰胺、聚乙烯基吡咯烷酮、各种聚醚和它们的共聚物以及聚丙烯酸和它们的盐。
可在本发明中使用其它制剂成分，例如染料、消泡剂、干燥剂等。这些成分为本领域技术人员熟知。
所述组合物还包括其他有效成分。
可以和本发明的无定形态苯唑氟草酮混合的合适的有效成分为，例如《世界农药新品种技术大全》，中国农业科学技术出版社，2010.9和这里引用的文献中的已知物质。例如以下提到的各种物质(备注：化合物的名称，或者为根据国际标准化组织(ISO)的普通名称，或者为化学名称，适当的时候有代号)：乙草胺、丁草胺、甲草胺、异丙草胺、异丙甲草胺、精异丙甲草胺、丙草胺、毒草胺、克草胺、萘丙酰草胺、R-左旋萘丙酰草胺、敌稗、苯噻酰草胺、双苯酰草胺、吡氟酰草胺、杀草胺、氟丁酰草胺、溴丁酰草胺、二甲噻草胺、高效二甲噻草胺、乙氧苯草胺、氟噻草胺、甲氧噻草胺、吡草胺、异恶草胺、高效麦草伏甲酯、高效麦草伏丙酯、二丙烯草胺、烯草胺、丁酰草胺、环丙草胺、氟磺酰草胺、庚酰草胺、异丁草胺、丙炔草胺、特丁草胺、二甲苯草胺、二甲草胺、落草胺、三甲环草胺、氯甲酰草胺、炔苯酰草胺、戊酰苯草胺、卡草胺、新燕灵、三环赛草胺、丁烯草胺、牧草胺、苄草胺、醌萍胺、苯氟磺胺、萘丙胺、乙酰甲草胺、萘草胺、噻草胺、吡氰草胺、苯草多克死、草克乐、氯酞亚胺、丁脒胺、氟吡草胺、莠去津、西玛津、扑草净、氰草净、西草净、莠灭净、扑灭津、异丙净、氟草净、特丁净、特丁津、三嗪氟草胺、环丙津、甘扑津、草达津、扑灭通、西玛通、叠氮净、敌草净、异戊乙净、环丙青津、灭莠津、另丁津、仲丁通、特丁通、甲氧丙净、氰草净、抑草津、可乐津、莠去通、灭草通、甘草津、三聚氰酸、Indaziflam、绿磺隆、甲磺隆、苄嘧磺隆、氯嘧黄隆、苯磺隆、噻磺隆、吡嘧黄隆、甲基二磺隆、甲基碘磺隆钠盐、甲酰氨基嘧磺隆、醚磺隆、醚苯磺隆、甲嘧磺隆、烟嘧磺隆、胺苯磺隆、酰嘧磺隆、乙氧嘧磺隆、环丙嘧磺隆、砜嘧磺隆、四唑嘧磺隆、啶嘧黄隆、单嘧磺隆、单嘧磺酯、氟唑磺隆、氟啶嘧磺隆、氟吡嘧磺隆、环氧嘧磺隆、唑吡嘧磺隆、氟嘧磺隆、丙苯磺隆、三氟丙磺隆、磺酰磺隆、三氟啶磺隆、氟胺磺隆、三氟甲磺隆、甲磺隆钠盐、氟吡磺隆、甲硫嘧磺隆、嘧苯胺磺隆、Propyrisulfuron(丙嗪嘧磺隆)、嗪吡嘧磺隆、三氟羧草醚、氟磺胺草醚、乳氟禾草灵、乙羧氟草醚、乙氧氟草醚、草枯醚、苯草醚、氯氟草醚乙酯、甲羧除草醚、三氟甲草醚、甲氧除草醚、三氟硝草醚、氟化除草醚、氟呋草醚、除草醚、甲草醚、二甲草醚、氟酯肟草醚、氟草醚酯、Halosafen、绿麦隆、异丙隆、利谷隆、敌草隆、莎扑隆、氟草隆、苯噻隆、甲基苯噻隆、苄草隆、磺噻隆、异恶隆、特丁噻草隆、炔草隆、氯溴隆、甲基杀草隆、酰草 隆、甲氧杀草隆、溴谷隆、甲氧隆、绿谷隆、灭草隆、环草隆、非草隆、氟硫隆、草不隆、枯草隆、草完隆、异草完隆、环莠隆、噻氟隆、丁噻隆、枯莠隆、对氟隆、甲胺噻唑隆、隆草特、三甲异脲、恶唑隆、Monisouron、Anisuron、Methiuron、Chloreturon、四氟隆、甜菜宁、甜菜宁-乙酯、甜菜安、磺草灵、特草灵、燕麦灵、苯胺灵、氯苯胺灵、二氯苄草酯、灭草灵、氯炔灵、Carboxazole、Chlorprocarb、Fenasulam、BCPC、CPPC、Carbasulam、丁草特、禾草丹、灭草猛、禾草特、野麦畏、哌草丹、禾草畏、稗草丹、环草敌、燕麦敌、菌达灭、乙硫草特、坪草丹、克草猛、苄草丹、仲草丹、硫烯草丹、草灭散、Isopolinate、Methiobencarb、2,4-滴丁酯、2甲4氯钠、2,4-滴异辛酯、2甲4氯异辛酯、2,4-滴钠盐、2,4-滴二甲胺盐、2甲4氯乙硫酯、2甲4氯、2,4-滴丙酸、高2,4-滴丙酸盐、2,4-滴丁酸、2甲4氯丙酸、2甲4氯丙酸盐、2甲4氯丁酸、2,4,5-涕、2,4,5-涕丙酸、2,4,5-涕丁酸、2甲4氯胺盐、麦草畏、抑草蓬、伐草克、赛松、三氯苯酸、氨二氯苯酸、甲氧三氯苯酸、禾草灵、吡氟禾草灵、精吡氟禾草灵、氟吡甲禾灵、高效吡氟氯禾灵、喹禾灵、精喹禾灵、恶唑禾草灵、精恶唑禾草灵、喔草酯、氰氟草酯、恶唑酰草胺、炔草酯、噻唑禾草灵、炔禾灵、羟戊禾灵、三氟禾草肟、异恶草醚、百草枯、敌草快、安磺灵、乙丁烯氟灵、异丙乐灵、甲磺乐灵、环丙氟灵、氨基丙氟灵、乙丁氟灵、氯乙氟灵、氨基乙氟灵、地乐灵、氯乙地乐灵、Methalpropalin、丙硝酚、草甘膦、莎稗膦、草铵膦、固杀草磷、甲基胺草磷、草硫膦、哌草膦、双丙氨膦、地散磷、抑草磷、蔓草磷、伐垅磷、双甲胺草磷、草特磷、咪唑烟酸、咪唑乙烟酸、咪唑喹啉酸、甲氧咪草烟、甲氧咪草烟铵盐、甲咪唑烟酸、咪草酯、氯氟吡氧乙酸、氯氟吡氧乙酸异辛酯、二氯吡啶酸、氨氯吡啶酸、三氯吡氧乙酸、氟硫草定、卤草定、三氯吡啶酚、噻草啶、氟啶草酮、氯氨吡啶酸、氟吡草腙、三氯吡氧乙酸丁氧基乙酯、Cliodinate、稀禾啶、烯草酮、噻草酮、禾草灭、环苯草酮、丁苯草酮、肟草酮、吡喃草酮、Buthidazole、嗪草酮、环嗪酮、苯嗪草酮、乙嗪草酮、Ametridione、Amibuzin、溴苯腈、辛酰溴苯腈、辛酰碘苯腈、碘苯腈、敌草腈、二苯乙腈、双唑草腈、羟敌草腈、Iodobonil、除草溴、唑嘧磺草胺、双氟磺草胺、五氟磺草胺、磺草唑胺、氯酯磺草胺、双氯磺草胺、啶磺草胺、氟草黄、双草醚、嘧啶肟草醚、环酯草醚、嘧草醚、嘧硫草醚、双环磺草酮、硝磺草酮、磺草酮、Tembotrione、Tefuryltrione、Bicyclopyrone、Ketodpiradox、异恶唑草酮、异恶氯草酮、Fenoxasulfone、Methiozolin、异丙吡草酯、吡草醚、吡唑特、野燕枯、苄草唑、吡草酮、吡氯草胺、Pyrasulfotole、苯唑草酮、Pyroxasulfone、唑草胺、氟胺草唑、杀草强、胺唑草酮、唑啶草酮、氟唑草酮、甲磺草胺、Bencarbazone、双苯嘧草酮、氟丙嘧草酯、除草定、异草定、环草啶、特草定、Flupropacil、吲哚酮草酯、氟烯草酸、丙炔氟草胺、炔草胺、酞苄醚、Flumezin、五氯酚(钠)、地乐酚、特乐酚、特乐酯、戊硝酚、二硝酚、氯硝酚、地乐施、地乐特、丙炔恶草酮、恶草酮、环戊 恶草酮、氟唑草胺、嗪草酸甲酯、四唑酰草胺、氟哒嗪草酯、杀草敏、溴莠敏、二甲达草伏、哒草醚、草哒酮、草哒松、哒草伏、Pyridafol、二氯喹啉酸、氯甲喹啉酸、苯达松、哒草特、恶嗪草酮、草除灵、异恶草酮、环庚草醚、异丙酯草醚、丙酯草醚、茚草酮、氯酸钠、茅草枯、三氯醋酸、一氯醋酸、六氯丙酮、四氟丙酸、吗草快、牧草快、溴酚肟、三唑磺、灭杀唑、呋草酮、呋草磺、乙呋草磺、嘧草胺、氯酞酸、氟咯草酮、稗草稀、丙烯醛、苯草灭、灭草环、燕麦酯、噻二唑草胺、棉胺宁、羟草酮、氨氯苯醌、甲氧苯酮、苯嘧磺草胺、氯酰草膦、三氯丙酸、Alorac、Diethamquat、Etnipromid、Iprymidam、Ipfencarbazone、Thiencarbazone-methyl、Pyrimisulfan、Chlorflurazole、Tripropindan、Sulglycapin、甲硫磺乐灵、Cambendichlor、环丙嘧啶酸、硫氰苯胺、解草酮、解草啶、解草安、解草唑、解草喹、解草腈、解草烷、解草胺腈、解草烯、吡唑解草酯、呋喃解草唑、肟草安、双苯噁唑酸、二氯丙烯胺、氟氯吡啶酯、DOW848、UBH-509、D489，LS 82-556、KPP-300、NC-324、NC-330、KH-218、DPX-N8189、SC-0744、DOWCO535、DK-8910、V-53482、PP-600、MBH-001、KIH-9201、ET-751、KIH-6127和KIH-2023。且经实验验证本无定形态苯唑氟草酮与上述列举的除草剂中的一种或多种复配施药具有明显的协同和增效作用。
优选地，所述其他有效成分包括但不限于：莠去津、特丁津、辛酰溴苯腈、烟嘧磺隆、氯吡嘧磺隆、氯氟吡氧乙酸、麦草畏、乙草胺、丁草胺、灭草松、吡氟酰草胺、胺唑草酮、嗪草酸甲酯、2甲4氯和嗪草酮中的一种或多种。
所述组合物中有效成分的总质量含量为75％以内，优选50％以内。
所述组合物的剂型为悬浮剂(SC)、可分散油悬浮剂(OD)、乳油(EC)、微乳剂(ME)、颗粒剂(GR)、悬乳剂(SE)或水分散粒剂(WDG)。
所述的无定形态苯唑氟草酮或所述的除草复配组合物在防除玉米田中禾本科杂草及部分阔叶杂草上的应用。
本发明的无定形态苯唑氟草酮相比A晶型，物理化学稳定性好，在55℃高温下储存两个月以内未发生晶型转变，纯度也基本未降低，同时水中溶解度增加一倍，苯唑氟草酮的无定形态以及与其它有效成分的复配组合物，对玉米田禾本科杂草及部分阔叶杂草均有非常好的防除效果，具有很好的应用前景。
附图说明
图1是本发明中的实施例1苯唑氟草酮A晶型的XRPD图谱。
图2是本发明中的实施例2无定形态苯唑氟草酮晶型的XRPD图谱。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上 述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
XRPD测定方法
仪器型号：Bruker D8advance，靶：Cu Kα(40kV，40mA)，样品到检测器距离：30cm，扫描范围：3°-40°(2θ值)，扫描步径：0.05s。
实施例1
参照CN 105503728 B方法制备得到苯唑氟草酮原药。再将3000克苯唑氟草酮原药置于10L的烧瓶中，加入乙酸乙酯5L，加热至50℃，搅拌至原料完全溶解，降温至0℃，静置2小时，过滤，30℃常压鼓风干燥5小时，得到苯唑氟草酮A晶型的粉末。或将溶剂挥发，至溶剂完全挥发完毕，也可得到苯唑氟草酮A晶型的粉末。
实施例2
将3000克苯唑氟草酮A晶型原药置于10L的烧瓶中，加入二氯甲烷7L，搅拌至原料完全溶解，加热至50℃，旋蒸溶剂，蒸发完毕后进行机械研磨，即可得到无定形态苯唑氟草酮的粉末。
物理化学稳定性实验
将实施例1得到的苯唑氟草酮A晶型和实施例2得到的无定形态苯唑氟草酮两种粉末，经过HPLC实测A晶型和无定形态含量均为95.0％，之后，将这两种粉末分别置于25℃、35℃、45℃和55℃烘箱里面，放置2个月进行热储实验，之后测试晶型类型和纯度，结果见下表1：
表1 苯唑氟草酮不同晶型的稳定性考察
Figure PCTCN2017084905-appb-000002
由表1可知，苯唑氟草酮A晶型和无定形态在不同的温度条件下均有良好的稳定性，尤其在55℃较高温度下，无定形态依然保持良好的物理化学稳定性，晶型未发生转变，纯度检测甚至略优于A晶型，具有重要意义。
水中溶解度测定
将实施例1得到的苯唑氟草酮A晶型和实施例2得到的无定形态苯唑氟草酮两种粉末，均溶解在纯水中，在25℃下震荡24h，使之充分溶解，之后用滤纸过滤，滤液再过0.22μm滤 膜，流动相溶解后用HPLC测定水中溶解度，结果见下表2：
由表2结果可见，苯唑氟草酮的无定形态相对比A晶型，溶解度有明显的增加。
表2 苯唑氟草酮不同晶型的水中溶解度测试结果
样品 纯水中溶解度(mg/L)
实施例2无定形态苯唑氟草酮 6.6
实施例1苯唑氟草酮A晶型 3.2
制剂加工和大田药效实验
将实施例1得到的苯唑氟草酮A晶型和实施例2得到的无定形态苯唑氟草酮，将按照如下配方，加工成相应的制剂，具体配方如下：
6％苯唑氟草酮OD
6％苯唑氟草酮+5％乳化剂十二烷基苯磺酸钙+8％乳化剂苯乙基酚聚氧乙烯醚+4％乳化剂蓖麻油聚氧乙烯醚+2.5％增稠剂有机膨润土+2％增稠剂气相法二氧化硅+20％分散介质大豆油+分散介质油酸甲酯补足
10％苯唑氟草酮SC
10％苯唑氟草酮+4％分散剂聚羧酸盐+2％润湿剂脂肪醇聚氧乙烯醚+0.25％增稠剂黄原胶+0.5％增稠剂羧甲基纤维素+5％防冻剂丙三醇+0.1％消泡剂有机硅油+水补足
25％苯唑氟草酮·莠去津OD
3％苯唑氟草酮+22％莠去津+6％乳化剂十二烷基苯磺酸钙+7％乳化剂苯乙基酚聚氧乙烯醚+5％乳化剂蓖麻油聚氧乙烯醚+2.5％增稠剂有机膨润土+2％增稠剂气相法二氧化硅+20％200#溶剂油+分散介质油酸甲酯补足
8％苯唑氟草酮·烟嘧磺隆OD
6％苯唑氟草酮+2％烟嘧磺隆+6％乳化剂十二烷基苯磺酸钙+7％乳化剂苯乙基酚聚氧乙烯醚+5％乳化剂脂肪醇聚氧乙烯醚+3％增稠剂有机膨润土+2％增稠剂气相法二氧化硅+20％溶剂癸酰胺+分散介质油酸甲酯补足
3.5％苯唑氟草酮·氯氟吡氧乙酸OD
1.5％苯唑氟草酮+2％氯氟吡氧乙酸+6％乳化剂十二烷基苯磺酸钙+7％乳化剂苯乙基酚聚氧乙烯醚+5％乳化剂脂肪醇聚氧乙烯醚+3％增稠剂有机膨润土+2％增稠剂气相法二氧化硅+10％分散介质菜籽油+分散介质油酸甲酯补足
28％苯唑氟草酮·特丁津WP
3％苯唑氟草酮+25％特丁津+10％分散剂木质素磺酸钠+3％润湿剂十二烷基硫酸钠+10％ 填料白炭黑+填料高岭土补足
30％苯唑氟草酮·丁草胺EC
3％苯唑氟草酮+27％丁草胺+20％环己酮+10％N-甲基吡咯烷酮+6％乳化剂十二烷基苯磺酸钙+12％乳化剂壬基酚聚氧乙烯醚+5％乳化剂苯乙基酚聚氧乙烯醚甲醛树脂缩合物+溶剂100#溶剂油补足
32％苯唑氟草酮·吡氟酰草胺SC
12％苯唑氟草酮+20％吡氟酰草胺+4％分散剂苯乙基酚聚氧乙烯醚磷酸酯三乙醇胺盐+2％润湿剂十二烷基苯磺酸钠+0.25％增稠剂黄原胶+0.5％增稠剂羧甲基纤维素+5％防冻剂丙三醇+0.1％消泡剂有机硅油+水补足
10％苯唑氟草酮·辛酰溴苯腈ME
3％苯唑氟草酮+7％辛酰溴苯腈+20％环己酮+5％乙醇+6％乳化剂十二烷基苯磺酸钙+12％乳化剂苯乙基酚聚氧乙烯醚+5％乳化剂苯乙基酚聚氧乙烯醚甲醛树脂缩合物+水补足
16％苯唑氟草酮·麦草畏EC
6％苯唑氟草酮+10％麦草畏+10％环己酮+10％N-甲基吡咯烷酮+6％乳化剂十二烷基苯磺酸钙+12％乳化剂壬基酚聚氧乙烯醚+2％乳化剂苯乙基酚聚氧乙烯醚甲醛树脂缩合物+溶剂100#溶剂油补足
40％苯唑氟草酮·胺唑草酮WDG
24％苯唑氟草酮+16％胺唑草酮+10％分散剂木质素磺酸钠+3％润湿剂十二烷基硫酸钠+10％填料白炭黑+填料高岭土补足
4.5％苯唑氟草酮·氯吡嘧磺隆WP
3％苯唑氟草酮+1.5％氯吡嘧磺隆+2％润湿剂十二烷基硫酸钠+4％分散剂萘磺酸酯-甲醛缩合物+填料硅藻土补足
23％苯唑氟草酮·乙草胺SE
3％苯唑氟草酮+20％丁草胺+4％分散剂苯乙基酚聚氧乙烯醚磷酸酯三乙醇胺盐+6％乳化剂壬基酚聚氧乙烯醚+0.2％增稠剂黄原胶+0.5％增稠剂硅酸镁铝+5％防冻剂丙三醇+0.1％消泡剂有机硅油+水补足
大田效果试验：玉米3-5叶，稗草、马唐3-4叶期，手动喷雾器，兑水量30公斤/667m2，采用茎叶喷雾均匀喷雾，小区面积50平方米，每处理重复4次施药后45天调查平均株防效(目测)效果如下，见表3。
表3 不同晶型的苯唑氟草酮制剂防除玉米直播田杂草效果(％)——施药45d后防效
Figure PCTCN2017084905-appb-000003
Figure PCTCN2017084905-appb-000004
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。

Claims (10)

  1. 一种无定形态苯唑氟草酮，其特征在于，经X-射线粉末衍射检测是以无定型的形式存在的。
  2. 根据权利要求1所述的一种无定形态苯唑氟草酮，其特征在于，X-射线粉末衍射图谱上没有尖锐的衍射峰，优选地，其X射线粉末衍射图谱基本上如图2所示。
  3. 如权利要求1或2所述无定形态苯唑氟草酮的制备方法，其特征在于，包括以下步骤：将三唑磺草酮搅拌溶解在二氯甲烷中，于40-60℃减压旋转蒸发溶剂，优选温度为45-50℃，之后经机械研磨，得到无定形态。
  4. 一种除草复配组合物，其特征在于：包括如权利要求1或2所述的无定形态苯唑氟草酮有效成分和助剂。
  5. 根据权利要求4所述的除草复配组合物，其特征在于：所述助剂选自溶剂、固体稀释剂、乳化剂、润湿剂、分散剂、防冻剂、消泡剂和增稠剂中的一种或多种。
  6. 根据权利要求4或5所述的除草复配组合物，其特征在于，所述组合物还包括其他有效成分。
  7. 根据权利要求6所述的除草复配组合物，其特征在于，所述其他有效成分选自莠去津、特丁津、辛酰溴苯腈、烟嘧磺隆、氯吡嘧磺隆、氯氟吡氧乙酸、麦草畏、乙草胺、丁草胺、灭草松、吡氟酰草胺、胺唑草酮、嗪草酸甲酯、2甲4氯和嗪草酮中的一种或多种。
  8. 根据权利要求6所述的除草复配组合物，其特征在于，所述组合物中有效成分的总质量含量为75％以内，优选50％以内。
  9. 根据权利要求4所述的除草复配组合物，其特征在于：所述组合物的剂型为悬浮剂、可分散油悬浮剂、乳油、微乳剂、颗粒剂、悬乳剂或水分散粒剂。
  10. 如权利要求1或2所述的无定形态苯唑氟草酮或权利要求4-9任意一项所述的除草复配组合物在防除玉米田中禾本科杂草及部分阔叶杂草上的应用。
PCT/CN2017/084905 2017-05-02 2017-05-18 无定形态苯唑氟草酮及其制备方法和用途 WO2018201523A1 (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4043456A1 (en) 2021-02-11 2022-08-17 Rotam Agrochem International Company Limited Crystalline form of pyroxasulfone, methods for its preparation and use of the same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106966983B (zh) * 2017-05-02 2019-07-02 青岛清原化合物有限公司 无定形态苯唑氟草酮及其制备方法和用途
CN113016810B (zh) * 2017-09-19 2021-11-16 青岛清原抗性杂草防治有限公司 一种含三唑磺草酮的除草组合物及其应用
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
CN111362917B (zh) * 2018-12-25 2021-03-12 青岛清原化合物有限公司 一种无定形态环吡氟草酮一异丙胺盐及其制备方法和用途
CN111362913B (zh) * 2018-12-25 2021-03-12 青岛清原化合物有限公司 一种无定形态环吡氟草酮三乙醇胺盐及其制备方法和用途

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105831123A (zh) * 2016-04-15 2016-08-10 青岛清原抗性杂草防治有限公司 一种玉米田除草组合物及其应用
CN106106474A (zh) * 2016-06-21 2016-11-16 泰安市农业科学研究院 一种玉米田除草组合物及其用途
CN106135220A (zh) * 2016-06-22 2016-11-23 泰安市农业科学研究院 一种玉米田除草组合物
CN106577715A (zh) * 2016-11-01 2017-04-26 广东中迅农科股份有限公司 含有苯唑氟草酮和烟嘧磺隆以及氯氟吡氧乙酸的农药组合物
CN106665599A (zh) * 2016-10-11 2017-05-17 泰安市农业科学研究院 含有苯唑氟草酮和异恶唑草酮的除草剂组合物及其应用
CN106966983A (zh) * 2017-05-02 2017-07-21 青岛清原化合物有限公司 无定形态苯唑氟草酮及其制备方法和用途

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105831123A (zh) * 2016-04-15 2016-08-10 青岛清原抗性杂草防治有限公司 一种玉米田除草组合物及其应用
CN106106474A (zh) * 2016-06-21 2016-11-16 泰安市农业科学研究院 一种玉米田除草组合物及其用途
CN106135220A (zh) * 2016-06-22 2016-11-23 泰安市农业科学研究院 一种玉米田除草组合物
CN106665599A (zh) * 2016-10-11 2017-05-17 泰安市农业科学研究院 含有苯唑氟草酮和异恶唑草酮的除草剂组合物及其应用
CN106577715A (zh) * 2016-11-01 2017-04-26 广东中迅农科股份有限公司 含有苯唑氟草酮和烟嘧磺隆以及氯氟吡氧乙酸的农药组合物
CN106966983A (zh) * 2017-05-02 2017-07-21 青岛清原化合物有限公司 无定形态苯唑氟草酮及其制备方法和用途

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4043456A1 (en) 2021-02-11 2022-08-17 Rotam Agrochem International Company Limited Crystalline form of pyroxasulfone, methods for its preparation and use of the same

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