WO2018192043A1 - 三唑磺草酮b晶型及其制备方法和用途 - Google Patents

三唑磺草酮b晶型及其制备方法和用途 Download PDF

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WO2018192043A1
WO2018192043A1 PCT/CN2017/084806 CN2017084806W WO2018192043A1 WO 2018192043 A1 WO2018192043 A1 WO 2018192043A1 CN 2017084806 W CN2017084806 W CN 2017084806W WO 2018192043 A1 WO2018192043 A1 WO 2018192043A1
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crystal form
crystal
agent
triazolone
herbicidal
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PCT/CN2017/084806
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English (en)
French (fr)
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赵德
陈志祥
林贝贝
张兆真
彭学岗
张景远
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青岛清原化合物有限公司
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Publication of WO2018192043A1 publication Critical patent/WO2018192043A1/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
    • 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

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  • the invention belongs to the technical field of herbicide crystallization process, and particularly relates to a triazolone B crystal form, a preparation method thereof and use thereof.
  • triazosin 4-(2-chloro-3-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-4-(methylsulfonyl)benzene Acyl)-1,3-dimethyl-1H-pyrazol-5-yl-1,3-dimethyl-1H-pyrazole-4-carboxylate
  • Triazolone is a newly developed HPPD inhibitor herbicide for post-emergence stem and leaf treatment of rice fields. It has excellent biological activity and can effectively control a variety of malignant weeds in rice fields. Compound patents have been authorized, and the authorization number is: CN 105503728B.
  • 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.
  • triazosinone is the newly developed drug, there is no report on its crystal form in various literatures and patents. Studies have found that in most cases, triazosin is present in Form A.
  • the invention provides a novel herbicide triazolone B crystal form, a preparation method thereof and a use thereof, and the triazolone B crystal form has good stability and good control effect on weeds, and can be used for preventing and removing impurities after rice seedlings grass.
  • triazosulfone is prepared by the method of CN 105503728B. Specifically, it was disclosed that 2.1 g (0.005 mol) of Compound a was weighed into a 100 mL single-necked flask, and 15 mL of acetonitrile and 1.0 g (0.010 mol) of triethylamine were added, and stirring was started under ice water bath. 1.0 g (0.006 mol) of 1,3-dimethylpyrazole-4-carbonyl chloride was dissolved in 10 mL of acetonitrile and placed in a dropping funnel, and dropwise addition was started under ice water bath conditions.
  • Examples 2 to 13 respectively illustrate the synthesis of the compound 02 to the compound 13 in Table 1, which is similar to the first embodiment, and the triazolone described in the present application is the compound described in Example 3.
  • the prepared triazolone is a crystal form, and the triazolone is dissolved in a series of solvents: methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, acetonitrile, tetrahydrofuran, nitromethane.
  • a triazolone B crystal form having an X-ray powder diffraction pattern at diffraction angles 2 ⁇ of 7.1, 7.3, 9.6, 11.8, 13.4, 14.2, 14.6, 14.9, 18.2, 18.8, 19.1, 19.6, 19.9, 21.0 , 21.4, 21.7, 22.6, 24.1, 24.4, 25.1, 25.8, 26.4, 27.2, 27.7, 28.0, 28.6, 29.4, 32.1, 34.7, 35.9, 36.8, 38.8, 39.3, 39.7 degrees with characteristic peaks, where 2 ⁇ error range Within ⁇ 0.2°.
  • I/I 0 values are 100, 21.3, 11.6, 14.9, 10.1, 43.5, 5.1, 6.4, 46.4, 9.4, 29.6, 8.1, 18.9, 32.9, 51.6, 6.8, 8.4, 18.7, 6.1, 8.0, 10.5, respectively. 6.9, 16.4, 13.6, 10.9, 58.9, 7.6, 7.1, 7.9, 14.8, 4.5, 4.6, 4.6, 5.3.
  • its X-ray powder diffraction pattern is substantially as shown in FIG.
  • the preparation method of the triazolone B crystal form comprises the following steps: dissolving triazosulfone in methylene chloride, heating to complete dissolution, cooling to 25 ° C, allowing to stand for crystallization and filtering, 25 ° C
  • the crystal obtained after internal drying is a B crystal form
  • the triazosulfone is dissolved in dichloromethane, heated to complete dissolution, and then cooled to 25 ° C, naturally volatilized until the solvent is completely evaporated, and the obtained crystal is B crystal.
  • a herbicidal formulation comprising the triazolone 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 triazolone B crystal form 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, isoxacillin,
  • other active ingredients include, but are not limited to, isoproturon, dipyridamole, bentazone, cyhalofoprin, butachlor, quinclorac, mesotrione, oxazolidine, octanoyl bromide Nitrile, clomazone, saricin and oxadiazon.
  • the total mass content of the active ingredient 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
  • triazolone B crystal form or the herbicidal compound composition for controlling grass weeds and some broad-leaved weeds in rice fields.
  • the triazolone B crystal form of the invention has good stability, and the B crystal form or the compound composition with other active ingredients has good control effects on the paddy weeds and some broad-leaved weeds in rice fields. The effect is obviously better than the A crystal form.
  • Figure 1 is an XRPD pattern of the crystalline form of triazosulfone A of Example 1 in the present invention.
  • Figure 2 is an XRPD pattern of the crystal form of the triazosulfone B of 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 triazolone is prepared according to the method of CN 105503728B. Then 3000 g of triazosinone was placed in a 10 L flask, acetone 5 L was added, heated to 50 ° C, stirred until the starting material was completely dissolved, cooled to 0 ° C, allowed to stand for 2 hours, filtered, 30 ° C atmospheric drum The mixture was air-dried for 5 hours to obtain a powder of the triazolone A crystal form. Alternatively, the solvent may be volatilized until the solvent has completely evaporated, and a powder of the triazolone A crystal form may also be obtained.
  • triazosinone A crystal form into a 10 L flask, add 6 L of dichloromethane, stir while heating until the raw material is completely dissolved. After the raw material is completely dissolved, stop heating, gradually reduce the temperature to about 10 ° C, and let stand. After 1 hour, filtration and drying under normal pressure at a temperature of 15 ° C for 5 hours, a powder of triazolone B crystal form was obtained. It can also be naturally volatilized at 25 ° C until the complete evaporation of methylene chloride to obtain a triazolone B crystal powder.
  • Table 2 The effect of different crystalline forms of triazosulfone on weed control in rice field (%) - control effect after 45 days of application
  • test plot valerian showed some resistance to quinclorac, and 150g/hm 2 quinclorac was ⁇ 10% effective against valerian.

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Abstract

本发明属于除草剂结晶工艺技术领域，具体涉及一种三唑磺草酮B晶型及其制备方法和用途。所述三唑磺草酮B晶型的X-射线粉末衍射谱图在衍射角2θ为7.1、7.3、9.6、11.8、13.4、14.2、14.6、14.9、18.2、18.8、19.1、19.6、19.9、21.0、21.4、21.7、22.6、24.1、24.4、25.1、25.8、26.4、27.2、27.7、28.0、28.6、29.4、32.1、34.7、35.9、36.8、38.8、39.3、39.7度处具有特征峰，其中2θ误差范围在±0.2°内。本发明的三唑磺草酮B晶型稳定性好，且B晶型或与其它有效成分的复配组合物，对水稻田禾本科杂草及部分阔叶杂草均有较好的防除效果，效果明显优于A晶型。

Description

三唑磺草酮B晶型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，具体涉及一种三唑磺草酮B晶型及其制备方法和用途。
背景技术
三唑磺草酮的化学名称：4-(2-氯-3-((3,5-二甲基-1H-吡唑-1-基)甲基)-4-(甲磺酰基)苯甲酰基)-1,3-二甲基-1H-吡唑-5-基-1,3-二甲基-1H-吡唑-4-甲酸酯
结构式：
Figure PCTCN2017084806-appb-000001
三唑磺草酮是新研发的水稻田苗后茎叶处理的HPPD抑制剂类除草剂，具有优异的生物活性，可以有效防除水稻田多种恶性杂草，化合物专利已被授权，授权公告号：CN 105503728B。
多晶型现象是指固体物质以两种或两种以上的不同空间排列方式，形成的具有不同物理化学性质的固体状态的现象。在药物研究领域，多晶型包括了有机溶剂化物、水合物等多组分晶体形式。药物多晶现象在药物开发过程中广泛存在，是有机小分子化合物固有的特性。理论上小分子药物可以有无限多的晶体堆积方式-多晶型。多晶型现象不光受到分子本身的空间结构和官能基团性能，分子内和分子间的相互作用等内在因素的控制，它还受药物合成工艺设计、结晶和纯化条件、制剂辅料选择、制剂工艺路线和制粒方法、以及储存条件、包装材料等诸方面因素的影响。不同晶型具有不同的颜色、熔点、溶解、溶出性能、化学稳定性、反应性、机械稳定性等，这些物理化学性能或可加工性能有时直接影响到药物的安全、有效性能。因此晶型研究和控制成为药物研发过程中的重要研究内容。
由于三唑磺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。经研究发现大多数情况下，三唑磺草酮都以A晶型存在。
发明内容
本发明提供了一种新型除草剂三唑磺草酮B晶型及其制备方法和用途，三唑磺草酮B晶型稳定性好，对杂草防治效果好，可用于水稻田苗后防除杂草。
本发明的技术方案，三唑磺草酮参照CN 105503728B中的方法制备。其中具体公开了，称量2.1g(0.005mol)化合物a于100mL单口烧瓶中，加入15mL乙腈和1.0g(0.010mol)三乙胺，冰水浴条件下开启搅拌。称量1.0g(0.006mol)1,3-二甲基吡唑-4-甲酰氯溶于10mL乙腈并置于滴液漏斗中，冰水浴条件下开始滴加。HPLC跟踪反应至化合物a反应完全。反应结束后，加入100mL水和100mL乙酸乙酯，萃取分去水层，有机层用100mL饱和食盐水洗涤2次后经无水硫酸钠干燥，旋蒸除去有机溶剂，得到棕黄色固体，经柱层析提纯后得到1.5g浅黄色粉末状固体。即为化合物01。HPLC含量93.9％，收率53.1％。反应式见下图：
Figure PCTCN2017084806-appb-000002
实施例2至实施例13分别说明表1中化合物02至化合物13的合成方法，其与实施例1类似，本申请所述的三唑磺草酮即为实施例3所述的化合物。
制备得到的三唑磺草酮原药为A晶型，同时将三唑磺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、和水等等，搅拌至完全溶解，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B晶型。
一种三唑磺草酮B晶型，X-射线粉末衍射谱图在衍射角2θ为7.1、7.3、9.6、11.8、13.4、14.2、14.6、14.9、18.2、18.8、19.1、19.6、19.9、21.0、21.4、21.7、22.6、24.1、24.4、25.1、25.8、26.4、27.2、27.7、28.0、28.6、29.4、32.1、34.7、35.9、36.8、38.8、39.3、39.7度处具有特征峰，其中2θ误差范围在±0.2°内。对应的I/I0值分别为100、21.3、11.6、14.9、10.1、43.5、5.1、6.4、46.4、9.4、29.6、8.1、18.9、32.9、51.6、6.8、8.4、18.7、6.1、8.0、10.5、6.9、16.4、13.6、10.9、58.9、7.6、7.1、7.9、14.8、4.5、4.6、4.6、5.3。
优选地，其X射线粉末衍射图谱基本上如图2所示。
所述三唑磺草酮B晶型的制备方法，包括以下步骤：将三唑磺草酮溶解在二氯甲烷中，加热至完全溶解之后，降温至25℃内静置结晶并过滤，25℃内干燥后得到的结晶物为B晶型；
或者，将三唑磺草酮溶解在二氯甲烷中，加热至完全溶解之后，降温至25℃内，自然挥发至溶剂完全挥发完毕，得到的结晶物为B晶型。
一种除草复配组合物，包括所述三唑磺草酮B晶型和助剂。
优选地，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。
可以和本发明的三唑磺草酮B晶型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。且经实验验证本三唑磺草酮B晶型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，其它有效成分包括但不限于：异丙隆、敌稗、灭草松、氰氟草酯、丁草胺、二氯喹啉酸、硝磺草酮、双唑草腈、辛酰溴苯腈、异噁草松、莎稗磷和唑草酮。
所述组合物中有效成分的总质量含量为75％以内，优选为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)。
所述的三唑磺草酮B晶型或所述的除草复配组合物在防除水稻田中禾本科杂草及部分阔叶杂草上的应用。
本发明的三唑磺草酮B晶型稳定性好，且B晶型或与其它有效成分的复配组合物，对水稻田禾本科杂草及部分阔叶杂草均有较好的防除效果，效果明显优于A晶型。
附图说明
图1是本发明中实施例1三唑磺草酮A晶型的XRPD图谱。
图2是本发明中实施例2三唑磺草酮B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 105503728B方法制备得到三唑磺草酮原药。再将3000克三唑磺草酮原药置于10L的烧瓶中，加入丙酮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，得到三唑磺草酮A晶型的粉末。或将溶剂挥发，至溶剂完全挥发完毕，也可得到三唑磺草酮A晶型的粉末。
实施例2
将3000克三唑磺草酮A晶型原药置于10L的烧瓶中，加入二氯甲烷6L，加热搅拌至原料完全溶解，待原料完全溶解后停止加热，逐步降温至10℃左右，静置1小时，过滤，15℃温度下常压鼓风干燥5小时，得到三唑磺草酮B晶型的粉末。也可以在25℃内自然挥发，至二氯甲烷完全挥发完毕，得到三唑磺草酮B晶型粉末。
物理化学稳定性实验
将实施例1得到的三唑磺草酮A晶型和实施例2得到的三唑磺草酮B晶型粉末，经过HPLC实测A晶型和B晶型含量均为96.0％左右，之后，将这两种晶型的原药分别置于25℃、40℃、55℃和70℃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1三唑磺草酮不同晶型的稳定性考察
Figure PCTCN2017084806-appb-000003
由表1可知，三唑磺草酮A晶型和B晶型在不同的温度条件下均有良好的稳定性，尤其在70℃较高温度下，晶型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，具有很好的应用前景。
制剂加工和大田药效实验
将实施例1得到的三唑磺草酮A晶型和实施例2得到的三唑磺草酮B晶型，按照如下配方，加工成制剂，具体配方如下：
5％三唑磺草酮OD
5％三唑磺草酮+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
30％三唑磺草酮·敌稗OD
5％三唑磺草酮+25％敌稗+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
25％三唑磺草酮·二氯喹啉酸WP
5％三唑磺草酮+20％二氯喹啉酸+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
35％三唑磺草酮·丁草胺EC
5％三唑磺草酮+30％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
18％三唑磺草酮·氰氟草酯OD
3％三唑磺草酮+15％氰氟草酯+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
38％三唑磺草酮·灭草松WDG
4％三唑磺草酮+34％灭草松+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
8％三唑磺草酮·异丙隆SC
4％三唑磺草酮+4％异丙隆+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
5％三唑磺草酮·双唑草腈OD(4+1)
4％三唑磺草酮+1％双唑草腈+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+2％增稠剂有机膨润土+2％增稠剂气相法二氧化硅+分散介质油酸甲酯补足
5％三唑磺草酮·胺唑草酮GR
4％三唑磺草酮+1％胺唑草酮+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
38％三唑磺草酮·丙草胺SE(8+30)
8％三唑磺草酮+30％丙草胺+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
12％三唑磺草酮·异噁草松EC
4％三唑磺草酮+8％异噁草松+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
16％三唑磺草酮·辛酰溴苯腈ME
5％三唑磺草酮+11％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
7％三唑磺草酮·硝磺草酮SC
6％三唑磺草酮+1％硝磺草酮+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
9％三唑磺草酮·氯氟吡啶酯OD
8％三唑磺草酮+1％氯氟吡啶酯+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+2％增稠剂有机膨润土+2％增稠剂气相法二氧化硅+分散介质油酸甲酯补足
8％三唑磺草酮·唑草酮OD
7％三唑磺草酮+1％氯氟吡啶酯+8％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+分散介质油酸甲酯补足
大田效果试验：水稻3叶后，稗草(湖南长沙采集种子)、千金子(湖北公安采集种子)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2。
表2不同晶型的三唑磺草酮防除水稻直播田杂草效果(％)——施药45d后防效
Figure PCTCN2017084806-appb-000004
Figure PCTCN2017084806-appb-000005
Figure PCTCN2017084806-appb-000006
注：试验地块稗草对二氯喹啉酸表现一定的抗性，150g/hm2二氯喹啉酸对稗草防效<10％。
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. 一种三唑磺草酮B晶型，其特征在于：X-射线粉末衍射谱图在衍射角2θ为7.1、7.3、9.6、11.8、13.4、14.2、14.6、14.9、18.2、18.8、19.1、19.6、19.9、21.0、21.4、21.7、22.6、24.1、24.4、25.1、25.8、26.4、27.2、27.7、28.0、28.6、29.4、32.1、34.7、35.9、36.8、38.8、39.3、39.7度处具有特征峰，其中2θ误差范围在±0.2°内。
  2. 根据权利要求1所述的一种三唑磺草酮B晶型，其特征在于：对应的I/I0值分别为100、21.3、11.6、14.9、10.1、43.5、5.1、6.4、46.4、9.4、29.6、8.1、18.9、32.9、51.6、6.8、8.4、18.7、6.1、8.0、10.5、6.9、16.4、13.6、10.9、58.9、7.6、7.1、7.9、14.8、4.5、4.6、4.6、5.3。
  3. 根据权利要求1或2所述的一种三唑磺草酮B晶型，其特征在于：X射线粉末衍射图谱基本上如图2所示。
  4. 如权利要求1-3任意一项所述三唑磺草酮B晶型的制备方法，其特征在于：包括以下步骤：将三唑磺草酮溶解在二氯甲烷中，加热至完全溶解之后，降温至25℃内静置结晶并过滤，25℃内干燥后得到的结晶物为B晶型。
  5. 如权利要求1-3任意一项所述三唑磺草酮B晶型的制备方法，其特征在于：包括以下步骤：将三唑磺草酮溶解在二氯甲烷中，加热至完全溶解之后，降温至25℃内，自然挥发至溶剂完全挥发完毕，得到的结晶物为B晶型。
  6. 一种除草复配组合物，其特征在于：包括权利要求1-3任意一项所述三唑磺草酮B晶型和助剂，优选地，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。
  7. 根据权利要求6所述的除草复配组合物，其特征在于：所述组合物还包括其他有效成分，优选地，所述其他有效成分选自异丙隆、敌稗、灭草松、氰氟草酯、丁草胺、二氯喹啉酸、硝磺草酮、双唑草腈、辛酰溴苯腈、异噁草松、莎稗磷和唑草酮中的一种或多种。
  8. 根据权利要求7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，优选为50％以内。
  9. 根据权利要求6-8任意一项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1-3任意一项所述的三唑磺草酮B晶型或权利要求6-9任意一项所述的除草复配组合物在防除水稻田中禾本科杂草及部分阔叶杂草上的应用。
PCT/CN2017/084806 2017-04-19 2017-05-18 三唑磺草酮b晶型及其制备方法和用途 WO2018192043A1 (zh)

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