WO2019223186A1 - 一种三唑磺草酮-水杨酸共晶及其制备方法和应用 - Google Patents

一种三唑磺草酮-水杨酸共晶及其制备方法和应用 Download PDF

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WO2019223186A1
WO2019223186A1 PCT/CN2018/105268 CN2018105268W WO2019223186A1 WO 2019223186 A1 WO2019223186 A1 WO 2019223186A1 CN 2018105268 W CN2018105268 W CN 2018105268W WO 2019223186 A1 WO2019223186 A1 WO 2019223186A1
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salicylic acid
crystal
trisulcotrione
acid
trisulconone
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PCT/CN2018/105268
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English (en)
French (fr)
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赵德
刘岩
林贝贝
张景远
范宗臣
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青岛清原化合物有限公司
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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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • 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 relates to the technical field of pesticide co-crystals, in particular to a triazosulone-salicylic acid co-crystal, and a preparation method and application thereof.
  • Drug co-crystals are based on the principle of supramolecular chemistry, that is, molecular recognition and supramolecular self-assembly through the interaction between molecules.
  • Self-assembly of the active pharmaceutical ingredient (API) with a suitable Cocrystal Former (CCF) via hydrogen bonding, or non-covalent bonds with saturation and directionality (such as van der Waals forces of aromatic hydrocarbons or benzene rings, conjugated Effect and halogen bond) is a new structure formed by the assembly, namely drug co-crystal.
  • Triazolam It is a newly developed HPPD inhibitor herbicide for the treatment of stems and leaves of rice fields after seedlings. It has excellent biological activity and can effectively control a variety of malignant weeds in rice fields.
  • the patents CN105503728B, CN107033086A, CN106946783A, and CN106977458A respectively disclose different forms of trisulcotrione, which has excellent weed control effects and can be used to control weeds in rice fields.
  • the present invention provides a triazolone-salicylic acid co-crystal, and a preparation method and application thereof.
  • the solubility of trisulconone in the co-crystal is far higher than that of trisulconone A, and the physicochemical properties are stable.
  • the bioassay data show that the trisulconone-salicylic acid co-crystal has a significant synergistic effect. .
  • trisulcotrione is prepared by referring to the method in CN105503728B.
  • Examples 2 to 13 illustrate the synthesis methods of compounds 02 to 13 in Table 1, respectively, which are similar to those in Example 1.
  • Triazosulone described in this application is the compound described in Example 3.
  • the triazosulone medicinal preparation is in Form A, and the triazosulone is dissolved in a series of solvents: methanol, ethanol, isopropanol, acetone, butanone, acetonitrile, tetrahydrofuran, and nitromethane.
  • Dissolve cool to stand for crystallization or slowly volatilize, and dry to obtain Form A.
  • the organic acids include: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caprylic acid, capric acid, and benzene.
  • Formic acid phenylacetic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, citric acid, salicylic acid, acetylsalicylic acid, benzenesulfonic acid, methanesulfonic acid, oxalic acid, tartaric acid, hard Fatty acid, palmitic acid, acrylic acid, etc., among which triazosulone-salicylic acid has outstanding eutectic properties.
  • the specific technical scheme is as follows:
  • a trisulcotrione-salicylic acid co-crystal includes a salicylic acid molecule and a trisulconone molecule.
  • the molar ratio of the trisulconone molecule and the salicylic acid molecule is 2: 1.
  • the trisulcotrione-salicylic acid co-crystal also includes two molecules of crystalline water, that is, the trisulconone molecule, the salicylic acid molecule, and the water molecule have a molar ratio of 2: 1: 2.
  • the X-ray powder diffraction spectrum has a diffraction angle 2 ⁇ of 7.9, 10.2, 11.5, 12.5, 12.7, 14.3, 14.7, 15.7, 17.6, 18.3, 19.7, 20.1, 21.0, 21.9, 23.5, 23.8, 25.6, 26.9, There are characteristic peaks at 28.7, 29.7, 30.1, and 31.4 degrees, where the 2 ⁇ error range is within ⁇ 0.2 °; preferably, the I / I 0 corresponding to the peak area is 25.1, 100.0, 15.7, 26.2, 18.0, 20.0, 28.5, 33.5, 37.3, 10.5, 44.7, 36.9, 18.8, 17.0, 82.5, 49.7, 51.7, 30.9, 19.8, 22.9, 21.5, 14.8.
  • the X-ray powder diffraction pattern is substantially as shown in FIG. 2.
  • the salicylic acid molecule and trisulcotrione molecule form hydrogen bonds with water molecules, respectively, and the trisulconone molecule forms halogen bonds with chlorine atoms and oxygen atoms.
  • a method for preparing trisulcotrione-salicylic acid cocrystal includes the following steps:
  • the stirring temperature is 20-80 ° C., the stirring time is 5-30 h, and the stirring speed is 100-1000 rpm.
  • the reaction temperature is 35-45 ° C., the reaction time is 10-20 hours, and the stirring speed is 250-400 rpm.
  • a herbicide composition comprising the trisulconone-salicylic acid co-crystal or trisulconone and salicylic acid according to (i); preferably, further comprising (ii) one or more additional Herbicides and / or safeners; more preferably, (iii) agrochemically acceptable formulation aids.
  • the specific preparation of the herbicidal composition is emulsifiable concentrate, aqueous suspension, microemulsion, suspoemulsion, aqueous emulsion, dispersible oil suspension, wettable powder or water-dispersible granule (dry suspension).
  • suitable active substances that can be mixed with the triazolone-salicylic acid co-crystal of the present invention are, for example, "World Encyclopedia of New Pesticides and Technologies", China Agricultural Science and Technology Press , 2010.9 and known substances in the literature cited here.
  • the herbicide active substances mentioned below can be mixed with triazolidin-salicylic acid co-crystals, (note: the name of the compound, or the common name according to the International Organization for Standardization (ISO), or the chemical name, as appropriate (Codenames are given at the time): Acetochlor, Butachlor, Acetochlor, Isoprochloride, Metolachlor, Smetochlor, Promechlor, Acetochlor, Chlortochlor, Naproxyl Surachlor, R-L-naphtholam, Diazepam, Phenanthramide, Bis-benzatochlor, Piracetamide, Mesalamine, Flubuteramide, Bromobutyramide, Dimethoate Methiopyramine, Dimethachlor, Ethoxybenzamide, Fluathiopyr, Methiolachlor, Pyributachlor, Clomachlor, High-Effect Chloride, High-Effect Chloride, Dimethochlor, Metochlor,
  • the safener is selected from the group consisting of pyraclostrobin (CAS number: 135590-91-9), detoxification quinone (CAS number: 99607-70-2), and dibenzoxazole acid (CAS No. 163520-33-0), cyprosulfamide (CAS number: 221667-31-8), gibberellic acid (CAS number: 77-06-5), furilazole (MON-13900, CAS number: 121776-33-8) , Metcamifen (CAS No .: 129531-12-0), cyclopropanesulfonamide (CAS No .: 154350-29-5), naphthalenedicarboxylic anhydride (NA, CAS No .: 34314-32-4), clotrimone ( CAS number: 37764-25-3), R-28725 (CAS number: 39089-45-7), AD-67 (CAS number: 71526-07-3), CGA-154281 (Benoxacor, CAS number: 98730-04 -2
  • the auxiliary agent is selected from one or more of a solvent, a solid diluent, an emulsifier, a wetting agent, a dispersant, an antifreeze agent, a defoamer, and a thickener.
  • Selected solvents include, but are not limited to, polar solvents: water, N, N-dimethylamide, dimethylsulfoxide, N-alkylpyrrolidone, methanol, ethanol, ethylene glycol, isopropyl alcohol, ethylene glycol Butyl ether, propylene glycol methyl ether, etc .; Aromatic solvent oil series: toluene, xylene, 100th solvent oil, 150th solvent oil, 180th solvent oil, 200th solvent oil, etc .; vegetable oils: castor oil, linseed oil, sesame oil , Corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and their corresponding methylated vegetable oils, etc .; ketones: cyclopentanone, cyclohexanone, cyclooctanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, etc .; acetates: methyl acetate, ethyl
  • the solid diluent chosen 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 the water-insoluble solid diluent include, but are not limited to, clay, calcium carbonate, diatomaceous earth, white carbon black, calcium silicate, bentonite, magnesium aluminum silicate, kaolin, and the like.
  • Wetting agents include, but are not limited to, alkylsulfosuccinates, laurates, alkyl sulfates, phosphates, ethoxyfluorinated alcohols, ethoxylated silicones, alkylphenol ethoxylates , Benzene sulfonate, alkyl substituted benzene sulfonate, alkyl ⁇ -olefin sulfonate, naphthalene sulfonate, alkyl substituted naphthalene sulfonic acid alkali metal salt, naphthalene sulfonic acid alkali metal salt, and alkyl substitution Condensate of naphthalenesulfonate with formaldehyde, ethoxylate of alcohol.
  • Dispersants include, but are not limited to: sodium, calcium, and ammonium salts of ligninsulfonic acid; sodium and ammonium salts of maleic anhydride copolymers; sodium salts of condensed phenolsulfonic acid; naphthalenesulfonate-formaldehyde condensates ; Phosphate ester dispersant, polycarboxylate dispersant and so on.
  • Thickeners include, but are not limited to, guar gum, pectin, xanthan gum, alginate, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose.
  • Synthetic thickeners include derivatives of the aforementioned types, and also include polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, various polyethers and their copolymers, and polyacrylic acid and their salts.
  • formulation ingredients can be used in the present invention, such as dyes, defoamers, desiccants, and the like. These ingredients are well known to those skilled in the art.
  • the invention also relates to a method for controlling harmful plants, which comprises using a herbicidally effective amount of the trisulcotrione-salicylic acid co-crystal or the herbicide composition on plants or harmful plant areas.
  • triazolidin-salicylic acid co-crystal or herbicide composition for controlling harmful plants, preferably, it is used for controlling harmful plants in useful crops which are genetically modified crops or Crops processed by genome editing technology.
  • the present invention has the following excellent effects: the solubility of trisulcotrione in the co-crystal is increased by about ten times, far more than the trisulconone A crystal form, and the physical and chemical properties are stable.
  • the data show that triazulone-salicylic acid co-crystals have obvious synergistic effects on weeds such as Humulus japonicus and Qianjin.
  • FIG. 1 is an XRPD pattern of the triazolone A crystal form according to the present invention
  • FIG. 2 is an XRPD spectrum of the triazolidin-salicylic acid co-crystal according to the present invention
  • FIG. 3 is a schematic diagram of a molecular structure of trisulcotrione-salicylic acid co-crystal single crystal according to the present invention (a hydrogen atom is omitted);
  • FIG. 4 is a schematic diagram of a single-crystal unit cell structure of trisulcotrione-salicylic acid co-crystal according to the present invention.
  • FIG. 5 is a schematic diagram of single crystal molecular stacking of trisulcotrione-salicylic acid cocrystals according to the present invention.
  • triazosulone Refer to CN105503728B to prepare triazosulone. Or put 3000g trisulcotrione original medicine in a 10L flask, add 5L of acetone, heat to 50 ° C, stir until the raw materials are completely dissolved, lower the temperature to 0 ° C, leave it for 2 hours, filter, and 30 ° C atmospheric pressure drum It was air-dried for 5 hours to obtain a powder of triazolone A crystal form. Or, the solvent is volatilized until the solvent is completely volatilized, and a powder of the trisulconone A crystal form can also be obtained. According to the HPLC measurement, the trisulconone content is approximately 95%.
  • triazosulone A crystal original medicine in a 10L flask, add 54g salicylic acid, add 4.3L deionized water, heat to 40 ° C, adjust the stirring speed to 300rpm, stir the reaction for 15 hours, and then pump The solid was obtained by filtration, and trisulcotrione-salicylic acid co-crystals were obtained by drying at 50 ° C. According to HPLC measurement, the trisulconone content was approximately 77%.
  • trisulfazone-salicylic acid co-crystals can also be prepared, which will not be repeated here.
  • Instrument Type Bruker D8advance, target: Cu K ⁇ (40kV, 40mA) , a sample to detector distance: 30cm, scan range: 3 0 -40 0 (2 ⁇ values), scanning step diameter: 0.05s.
  • the XRPD pattern is shown in Figure 1-2. From Figure 2, it can be seen that the X-ray powder diffraction pattern of trisulcotrione-salicylic acid co-crystal has a diffraction angle 2 ⁇ of 7.896, 10.238, 11.479, 12.480, 12.724, 14.282.
  • Example 2 The trisulconone A crystal form obtained in Example 1 and the trisulconone-salicylic acid eutectic powder obtained in Example 2 were dissolved in pure water and shaken at 25 ° C. for 1 h to make It was fully dissolved to form a saturated solution, and then filtered with filter paper, and the filtrate was passed through a 0.22 ⁇ m filter membrane. After the mobile phase was dissolved, the triazosulone in water was measured by HPLC. The results are shown in Table 2 below:
  • Example 3 The trisulconone A crystal form obtained in Example 1 and the trisulconone-salicylic acid cocrystals obtained in Example 2 were placed in 25 ° C, 40 ° C, and 55 ° C ovens, respectively. The heat storage experiment was performed for 2 months, and then the purity of the active ingredients and the solubility in water were tested. The results are shown in Table 3 below:
  • Example 1 The trisulconone A crystal form obtained in Example 1 and the trisulconone-salicylic acid co-crystal obtained in Example 2 were processed into the corresponding formula based on the trisulconone content according to the following formula. Preparation, the specific formula is as follows:
  • Humulus scandens has certain resistance to quinclorac.
  • 105g / hm 2 of dichloroquinolinic acid has a control effect on Humulus lupulus ⁇ 10%.
  • the trisulconone-salicylic acid co-crystal preparations have a significantly higher control effect on yarrow and Qianjin Tetrazotrione A crystalline preparation.

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Abstract

涉及农药共晶技术领域，具体地说涉及一种三唑磺草酮-水杨酸共晶及其制备方法和应用。所述三唑磺草酮-水杨酸共晶包括水杨酸分子和三唑磺草酮分子，三唑磺草酮分子和水杨酸分子的摩尔比为2∶1，且还包括二分子结晶水。所述共晶中三唑磺草酮的溶解度提高约十倍，远超三唑磺草酮A晶型，且物理化学性质稳定，生测数据表明三唑磺草酮-水杨酸共晶针对稗草和千金子等杂草的药效增效明显。

Description

一种三唑磺草酮-水杨酸共晶及其制备方法和应用 技术领域
本发明涉及农药共晶技术领域，具体地说涉及一种三唑磺草酮-水杨酸共晶及其制备方法和应用。
背景技术
药物共晶是基于超分子化学原理，即通过分子间的相互协同作用进行的分子识别和超分子自组装。药物活性成分(API)与合适的共晶形成物(Cocrystal Former，CCF)通过氢键自组装，或者带有饱和性和方向性的非共价键(如芳烃或苯环的范德华力，共轭作用和卤键)组装形成的一种新型结构，即药物共晶。
三唑磺草酮
Figure PCTCN2018105268-appb-000001
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。其中，专利CN105503728B、CN107033086A、CN106946783A和CN106977458A分别公开了不同形态的三唑磺草酮，杂草防治效果优异，可用于水稻田杂草的防除。
发明内容
基于上述现有技术，本发明提供一种三唑磺草酮-水杨酸共晶及其制备方法和应用。所述共晶中三唑磺草酮的溶解度远超三唑磺草酮A晶型，且物理化学性质稳定，生测数据表明三唑磺草酮-水杨酸共晶的药效增效明显。
本发明的技术方案，三唑磺草酮参照CN105503728B中的方法制备。其中[0136]-[0140]段具体公开了，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 PCTCN2018105268-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。另外，根据已有专利CN107033086A、CN106946783A和CN106977458A分别制备得到B晶型、C晶型和无定型态。
在此基础上，又研究了三唑磺草酮与各种有机酸的成盐或共晶，所述有机酸包括：甲酸、乙酸、丙酸、丁酸、戊酸、辛酸、癸酸、苯甲酸、苯乙酸、乙二酸、丙二酸、丁二酸、己二酸、马来酸、柠檬酸、水杨酸、乙酰水杨酸、苯磺酸、甲磺酸、草酸、酒石酸、硬脂酸、软脂酸和丙烯酸等，其中三唑磺草酮-水杨酸具有突出的共晶性能，具体的技术方案如下：
一种三唑磺草酮-水杨酸共晶，包括水杨酸分子和三唑磺草酮分子，优选地，三唑磺草酮分子和水杨酸分子的摩尔比为2∶1。
所述三唑磺草酮-水杨酸共晶还包括二分子结晶水，即三唑磺草酮分子、水杨酸分子、水分子三种分子摩尔比为2∶1∶2。
所述三唑磺草酮-水杨酸共晶为三斜晶系，空间群为P-1，晶胞参数为：
Figure PCTCN2018105268-appb-000003
Figure PCTCN2018105268-appb-000004
α＝67.376(4)°，β＝74.826(4)°，γ＝82.645(3)°。
所述X-射线粉末衍射谱图在衍射角2θ为7.9、10.2、11.5、12.5、12.7、14.3、14.7、15.7、17.6、18.3、19.7、20.1、21.0、21.9、23.5、23.8、25.6、26.9、28.7、29.7、30.1、31.4度处具有特征峰，其中2θ误差范围在±0.2°内；优选地，峰面积对应的I/I 0分别为25.1、100.0、15.7、26.2、18.0、20.0、28.5、33.5、37.3、10.5、44.7、36.9、18.8、17.0、82.5、49.7、51.7、30.9、19.8、22.9、21.5、14.8。
优选地，X射线粉末衍射图谱基本上如图2所示。
其中，水杨酸分子和三唑磺草酮分子分别与水分子形成氢键，且三唑磺草酮分子间氯原 子和氧原子形成卤键。
一种三唑磺草酮-水杨酸共晶的制备方法，包括以下步骤：
(1)称取三唑磺草酮、水杨酸于容器中，加去离子水；
(2)升温至所需温度，搅拌反应一定时间，之后抽滤并干燥得到固体即为三唑磺草酮-水杨酸共晶。
其中，搅拌温度为20-80℃，搅拌时间为5-30h，搅拌速度为100-1000rpm；优选地，反应温度为35-45℃，反应时间为10-20小时，搅拌速度为250-400rpm。
一种除草剂组合物，包括(i)所述的三唑磺草酮-水杨酸共晶或者三唑磺草酮和水杨酸；优选地，还包括(ii)一种或多种另外的除草剂和/或安全剂；更优选地，还包括(iii)农业化学上可接受的制剂助剂。
所述除草组合物的具体制剂为乳油、水悬浮剂、微乳剂、悬乳剂、水乳剂、可分散油悬浮剂、可湿性粉剂或水分散粒剂(干悬浮剂)。
在混配制剂或桶混制剂中，可以和本发明的三唑磺草酮-水杨酸共晶混合的合适的活性物质为，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。例如以下提到的除草剂活性物质可以和三唑磺草酮-水杨酸共晶混合，(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、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、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、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、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、DOW氯氟吡啶酯、砜吡草唑、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。
在进一步优选的实施形式中，所述安全剂选自吡唑解草酯(CAS号：135590-91-9)、解毒喹(CAS号：99607-70-2)、双苯恶唑酸(CAS号：163520-33-0)、cyprosulfamide(CAS号：221667-31-8)、赤霉酸(CAS号：77-06-5)、furilazole(MON-13900，CAS号：121776-33-8)、metcamifen(CAS号：129531-12-0)、环丙磺酰胺(CAS号：154350-29-5)、萘二甲酸酐(NA，CAS号：34314-32-4)、氯草烯安(CAS号：37764-25-3)、R-28725(CAS号：39089-45-7)、AD-67(CAS号：71526-07-3)、CGA-154281(Benoxacor，CAS号：98730-04-2)、CGA-43089(Cyometrinil，CAS号：78370-21-5)、Hoe-70542(Fenchlorazole，CAS号：103112-35-2)、解草啶(Fenclorim，CAS号：3740-92-9)、解草安(CAS号：2850-64-7)、BAS-145138(CAS号：79260-71-2)、2,4-D(有机酸类，CAS号：94-75-7)、喹啉衍生物、磺酰脲(胺)类安全剂和新型解毒剂T(主要成份4％Ti 4+)中的一种或多种。
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。
本发明还涉及一种控制有害植物的方法，包括将除草有效量的所述的三唑磺草酮-水杨酸共晶或所述的除草剂组合物使用在植物上或者有害植物区域。
以及所述三唑磺草酮-水杨酸共晶或除草剂组合物在控制有害植物上的用途，优选地，将其用于防除有用作物中的有害植物，所述有用作物为转基因作物或者基因组编辑技术处理过的作物。
与现有技术相比，本发明具有如下优异效果：所述共晶中三唑磺草酮的溶解度提高约十倍，远超三唑磺草酮A晶型，且物理化学性质稳定，生测数据表明三唑磺草酮-水杨酸共晶针对稗草和千金子等杂草的药效增效明显。
附图说明
图1为本发明所述三唑磺草酮A晶型的XRPD图谱；
图2为本发明所述三唑磺草酮-水杨酸共晶的XRPD图谱；
图3为本发明所述三唑磺草酮-水杨酸共晶单晶的分子结构示意图(省略氢原子)；
图4为本发明所述三唑磺草酮-水杨酸共晶的单晶晶胞结构示意图；
图5为本发明所述三唑磺草酮-水杨酸共晶的单晶分子堆积示意图。
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。
实施例1
参照CN105503728B方法制备得到三唑磺草酮原药。或者再将3000g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，经过HPLC实测，三唑磺草酮含量大致为95％左右。
实施例2
将200g三唑磺草酮A晶型原药置于10L的烧瓶中，加入水杨酸54g，加入4.3L去离子水，加热至40℃，搅拌转速调至300rpm，搅拌反应15小时，之后抽滤得到固体，50℃烘干即可得到三唑磺草酮-水杨酸共晶，经过HPLC实测，三唑磺草酮含量大致为77％左右。
另外，采用上述方法以三唑磺草酮B晶型、C晶型和无定型为原料，同样能制得三唑磺草酮-水杨酸共晶，在此不再赘述。
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 0-40 0(2θ值)，扫描步径：0.05s。
XRPD图谱如图1-2所示，由图2可知，三唑磺草酮-水杨酸共晶的X-射线粉末衍射谱图在衍射角2θ为7.896、10.238、11.479、12.480、12.724、14.282、14.680、15.720、17.561、18.320、19.740、20.120、21.018、21.919、23.517、23.820、25.577、26.900、28.701、29.682、30.098、31.362度处具有特征峰；峰面积对应的I/I 0分别为25.1、100.0、15.7、26.2、18.0、20.0、28.5、33.5、37.3、10.5、44.7、36.9、18.8、17.0、82.5、49.7、51.7、30.9、19.8、22.9、21.5、14.8。
培养单晶
称取实施例2中得到的三唑磺草酮-水杨酸共晶样品0.01g于锥形瓶中，加甲醇1mL，摇晃溶解至澄清溶液，之后缓慢挥发，培养得到片状单晶。
解单晶，所得单晶数据如下表1，结构如附图3-5所示，可以发现共晶中三唑磺草酮分子、水杨酸分子、水分子三种分子摩尔比为2∶1∶2，位置1是水杨酸分子、三唑磺草酮分子分别与水分子成氢键，位置2是三唑磺草酮分子间氯原子和氧原子之间形成的卤键，所以制备得到的是含二分子结晶水的三唑磺草酮-水杨酸共晶。
表1三唑磺草酮-水杨酸共晶单晶数据表
Figure PCTCN2018105268-appb-000005
水中溶解度测定
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-水杨酸共晶两种粉末，均溶解在纯水中，在25℃下震荡1h，使之充分溶解形成饱和溶液，之后用滤纸过滤，滤液再过0.22μm滤膜，流动相溶解后用HPLC测定三唑磺草酮水中溶解度，结果见下表2：
表2三唑磺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1三唑磺草酮A晶型 6.2
实施例2三唑磺草酮-水杨酸共晶 61.8
由表2结果可见，三唑磺草酮的-水杨酸共晶相对于A晶型，溶解度有明显的增加，增加了约十倍左右，而溶解度的增加有利于改善药物的吸收，提升药效。
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-水杨酸共晶两种粉末分别置于25℃、40℃、和55℃烘箱里面，放置2个月进行热储实验，之后测试有效成分的纯度和水中溶解度，结果见下表3：
表3三唑磺草酮不同晶型的稳定性考察
Figure PCTCN2018105268-appb-000006
由表3可知，三唑磺草酮A晶型和三唑磺草酮-水杨酸共晶在不同的温度条件下均有良好的稳定性，尤其在55℃高温下，历经两个月放置，依然保持良好的物理化学稳定性，且共晶的溶解度仍然保持在普通晶型A十倍左右的溶解度，具有重要意义。
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-水杨酸共晶，以三唑磺草酮的含量计，按照如下配方，加工成相应的制剂，具体配方如下：
6％三唑磺草酮OD
6％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
18％三唑磺草酮·氰氟草酯OD
6％三唑磺草酮+12％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
28％三唑磺草酮·二氯喹啉酸WP
8％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
10％三唑磺草酮·异丙隆OD
8％三唑磺草酮+2％异丙隆+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+10％200#溶剂油+分散介质油酸甲酯补足
28％三唑磺草酮·敌稗OD
3％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
9％三唑磺草酮·胺唑草酮OD
8％三唑磺草酮+1％胺唑草酮+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
36％三唑磺草酮·丙草胺ME
6％三唑磺草酮+30％丙草胺+20％环己酮+10％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
33％三唑磺草酮·丁草胺EC
3％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
6％三唑磺草酮·双唑草腈SC
4.5％三唑磺草酮+1.5％双唑草腈+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
15％三唑磺草酮·辛酰溴苯腈ME
5％三唑磺草酮+10％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
9％三唑磺草酮·氯氟吡啶酯EC
8％三唑磺草酮+1％氟氯吡啶酯+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
30％三唑磺草酮·灭草松WDG
5％三唑磺草酮+25％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
11％三唑磺草酮·硝磺草酮GR
9％三唑磺草酮+2％硝磺草酮+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
16％三唑磺草酮·异噁草松SE
12％三唑磺草酮+4％异噁草松+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
20％三唑磺草酮·莎稗磷OD
5％三唑磺草酮+15％莎稗磷+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
6％三唑磺草酮·唑草酮OD
4.5％三唑磺草酮+1.5％唑草酮+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+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)、千金子(湖北公安)3-4叶期，手动喷雾器，兑水量30公斤/667m 2，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4。
表4不同形态三唑磺草酮制剂防除水稻直播田杂草效果(％)——施药45d后防效
Figure PCTCN2018105268-appb-000007
Figure PCTCN2018105268-appb-000008
注：本试验中稗草对二氯喹啉酸具有一定抗性，105g/hm 2二氯喹啉酸对稗草防效<10％。
由此可见，相同条件下不同形态三唑磺草酮制剂防除水稻直播田杂草效果相比，三唑磺草酮-水杨酸共晶制剂对于稗草和千金子的防效明显高于三唑磺草酮A晶型制剂。
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-水杨酸共晶，其特征在于：所述共晶包括水杨酸分子和三唑磺草酮分子，优选地，三唑磺草酮分子和水杨酸分子的摩尔比为2∶1。
  2. 根据权利要求1所述的一种三唑磺草酮-水杨酸共晶，其特征在于，还包括二分子结晶水。
  3. 根据权利要求1或2所述的一种三唑磺草酮-水杨酸共晶，其特征在于，三唑磺草酮-水杨酸共晶为三斜晶系，空间群为P-1，晶胞参数为：
    Figure PCTCN2018105268-appb-100001
    Figure PCTCN2018105268-appb-100002
    α＝67.376(4)°，β＝74.826(4)°，γ＝82.645(3)°。
  4. 根据权利要求1-3任意一项所述的一种三唑磺草酮-水杨酸共晶，其特征在于，X-射线粉末衍射谱图在衍射角2θ为7.9、10.2、11.5、12.5、12.7、14.3、14.7、15.7、17.6、18.3、19.7、20.1、21.0、21.9、23.5、23.8、25.6、26.9、28.7、29.7、30.1、31.4度处具有特征峰，其中2θ误差范围在±0.2°内；优选地，峰面积对应的I/I 0分别为25.1、100.0、15.7、26.2、18.0、20.0、28.5、33.5、37.3、10.5、44.7、36.9、18.8、17.0、82.5、49.7、51.7、30.9、19.8、22.9、21.5、14.8。
  5. 根据权利要求1-4任意一项所述的一种三唑磺草酮-水杨酸共晶，其特征在于，X射线粉末衍射图谱基本上如图2所示。
  6. 如权利要求1-5任意一项所述的一种三唑磺草酮-水杨酸共晶的制备方法，其特征在于，包括以下步骤：
    (1)称取三唑磺草酮、水杨酸于容器中，加去离子水；
    (2)升温至所需温度，搅拌反应一定时间，之后抽滤并干燥得到固体即为三唑磺草酮-水杨酸共晶。
  7. 根据权利要求5所述的一种三唑磺草酮-水杨酸共晶的制备方法，其特征在于，搅拌温度为20-80℃，搅拌时间为5-30h，搅拌速度为100-1000rpm；优选地，反应温度为35-45℃，反应时间为10-20小时，搅拌速度为250-400rpm。
  8. 一种除草剂组合物，其特征在于，包括(i)权利要求1-5任意一项所述的三唑磺草酮-水杨酸共晶或者三唑磺草酮和水杨酸；优选地，还包括(ii)一种或多种另外的除草剂和/或安全剂；更优选地，还包括(iii)农业化学上可接受的制剂助剂。
  9. 一种控制有害植物的方法，其特征在于，包括将除草有效量的权利要求1-5任意一项所述的三唑磺草酮-水杨酸共晶或权利要求8所述的除草剂组合物使用在植物上或者有害植物区域。
  10. 如权利要求1-5任意一项所述的三唑磺草酮-水杨酸共晶或权利要求8所述的除草剂组合物在控制有害植物上的用途，优选地，将其用于防除有用作物中的有害植物，所述有用 作物为转基因作物或者基因组编辑技术处理过的作物。
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