CN111362918A - 环吡氟草酮一异丙胺盐b晶型及其制备方法和用途 - Google Patents

环吡氟草酮一异丙胺盐b晶型及其制备方法和用途 Download PDF

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CN111362918A
CN111362918A CN201811594741.1A CN201811594741A CN111362918A CN 111362918 A CN111362918 A CN 111362918A CN 201811594741 A CN201811594741 A CN 201811594741A CN 111362918 A CN111362918 A CN 111362918A
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连磊
赵德
彭学岗
金涛
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Qingdao Kingagroot Chemical Compound Co Ltd
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Abstract

本发明属于除草剂结晶工艺技术领域，具体涉及一种环吡氟草酮一异丙胺B晶型及其制备方法和用途。所述环吡氟草酮一异丙胺B晶型的X‑射线粉末衍射谱图在衍射角2θ为6.8°、7.5°、8.1°、8.3°、10.1°、10.7°、11.3°、12.4°、13.7°、15.0°、16.4°、17.0°、17.8°、18.6°、19.1°、19.7°、20.5°、20.9°、21.8°、23.1°、24.1°、24.5°、25.1°、26.1°、27.3°、27.7°、28.3°、28.9°、29.6°、30.2°、31.0°、31.8°、32.5°、33.0°、33.5°、34.8°、35.2°、37.3°、38.2°、39.0°、39.6°、40.9°、41.3°、41.9°、42.8°、43.3°、43.9°处具有特征峰，其中2θ误差范围在±0.2°内。本发明的环吡氟草酮一异丙胺B晶型物理化学稳定性好，溶解度大，生物活性较高，可用于防除杂草。

Description

环吡氟草酮一异丙胺盐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，具体涉及一种环吡氟草酮一异丙胺盐B晶型及其制备方法和用途。
背景技术
环吡氟草酮(结构式：
Figure BDA0001921102270000011
)是新研发的小麦田苗后茎叶处理的HPPD抑制剂类除草剂，具有优异的生物活性，可以有效防除小麦田多种恶性禾本科杂草，化合物专利已被授权，授权公告号：CN 105218449 B。
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。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。
发明内容
本发明提供了一种新型除草剂环吡氟草酮一异丙胺盐B晶型及其制备方法和用途。该晶型物理化学稳定性好，溶解度大，生物活性较高，可用于作物田中的常见杂草的防除。
本发明采用的技术方案如下：
一种环吡氟草酮一异丙胺盐B晶型，X-射线粉末衍射谱图在衍射角2θ为6.8°、7.5°、8.1°、8.3°、10.1°、10.7°、11.3°、12.4°、13.7°、15.0°、16.4°、17.0°、17.8°、18.6°、19.1°、19.7°、20.5°、20.9°、21.8°、23.1°、24.1°、24.5°、25.1°、26.1°、27.3°、27.7°、28.3°、28.9°、29.6°、30.2°、31.0°、31.8°、32.5°、33.0°、33.5°、34.8°、35.2°、37.3°、38.2°、39.0°、39.6°、40.9°、41.3°、41.9°、42.8°、43.3°、43.9°处具有特征峰，其中2θ误差范围在±0.2°内。
优选地，对应的I/I0分别为3.9、27.5、3.5、3.0、100.0、4.6、14.4、1.8、47.1、13.9、25.6、3.9、13.4、7.6、10.2、50.5、14.7、5.2、33.1、20.9、3.6、17.6、5.8、15.8、13.1、48.0、4.3、3.0、9.2、7.4、6.9、3.6、1.8、6.2、46.9、17.3、14.5、2.0、2.6、3.7、2.1、3.0、3.5、2.8、1.7、3.7、2.2。
更优选地，其X射线粉末衍射图谱基本上如图1所示。
所述环吡氟草酮一异丙胺盐B晶型的制备方法，包括以下步骤：将环吡氟草酮原药与一异丙胺盐反应，得到环吡氟草酮一异丙胺盐，之后将环吡氟草酮一异丙胺盐溶解在乙醇中，搅拌至完全溶解，之后加入1-10倍体积的正庚烷或乙醚，使溶液析出大量固体结晶，所得固体结晶经干燥，得到环吡氟草酮一异丙胺盐B晶型。
一种除草复配组合物，包括(i)所述环吡氟草酮一异丙胺盐B晶型；优选地，还包括(ii)一种或多种其他有效成分和/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。
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、羧甲基纤维素和硅酸镁铝等等。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。
可以和本发明的环吡氟草酮一异丙胺盐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-滴一异丙胺盐盐、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。且经实验验证本发明环吡氟草酮一异丙胺盐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，所述其他有效成分包括但不限于：吡氟酰草胺(CAS号：83164-33-4)、异噁唑草酮(CAS号：141112-29-0)、炔草酯(CAS号：105512-06-9)、唑啉草酯(CAS号：243973-20-8)、异丙隆(CAS号：34123-59-6)、绿麦隆(CAS号：15545-48-9)、辛酰溴苯腈(CAS号：1689-99-2)、嗪草酮(CAS号：21087-64-9)、哒草特(CAS号：55512-33-9)、氨唑草酮(CAS号：129909-90-6)、2甲4氯(CAS号：94-74-6)、氯氟吡氧乙酸(CAS号：69377-81-7)、氟氯吡啶酯(CAS号：943831-98-9)、麦草畏(CAS号：1918-00-9)、苯嘧磺草胺(CAS号：372137-35-4)、氟噻草胺(CAS号：142459-58-3)、精异丙甲草胺(CAS号：178961-20-1)、砜吡草唑(CAS号：447399-55-5)、二甲戊灵(CAS号：40487-42-1)、甲基二磺隆(CAS号：208465-21-8)、氟唑磺隆(CAS号：181274-17-9)、啶磺草胺(CAS号：422556-08-9)、苄草丹(CAS号：52888-80-9)及其衍生物中的一种或多种。
在本说明书的上下文中，如果使用活性化合物的通用名称的缩写形式，则在每种情况下包括所有的常规衍生物，例如酯和盐，以及异构体，特别是光学异构体，特别是一种或多种市售形式。如果通用名称表示酯或盐，则在每种情况下还包括所有其他的常规衍生物，例如其他的酯和盐、游离酸和中性化合物，以及异构体，特别是光学异构体，特别是一种或多种市售形式。给出的化合物的化学名称表示至少一种被通用名称涵盖的化合物，通常是优选的化合物。在磺酰胺如磺酰脲的情况下，盐还包括通过阳离子与磺酰胺基团中的氢原子交换而形成的盐。例如，2甲4氯衍生物包含但不限于：2甲4氯钠盐、钾盐、二甲铵盐、异丙胺盐等，以及2甲4氯甲酯、乙酯、异辛酯、乙硫酯等。
在本发明的上下文中，化合物的盐优选为各自的碱金属盐、碱土金属盐或铵盐的形式，优选为各自的碱金属盐的形式，更优选为各自的钠盐或钾盐的形式，最优选为各自的钠盐的形式。
所述组合物中有效成分的总质量百分含量占总量的1-95％。
所述安全剂优选双苯噁唑酸(CAS：163520-33-0)、cyprosulfamide(CAS：221667-31-8)、吡唑解草酯(CAS：135590-91-9)、解毒喹(CAS：99607-70-2)、赤霉酸(CAS：7-06-5)、furilazole(CAS：121776-33-8)、metcamifen(CAS：129531-12-0)中的一种或多种。
所述组合物的剂型为水悬浮剂(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)。
本发明还提供了一种控制作物中杂草的方法，包括将除草有效量的所述的环吡氟草酮一异丙胺盐B晶型或所述的除草复配组合物使用在作物上或者杂草区域。
本发明还提供了所述的环吡氟草酮一异丙胺盐B晶型或所述的除草复配组合物在控制杂草上的用途；优选地，将其用于防除有用作物中的杂草，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。
优选地，所述作物为小麦，所述杂草为禾本科杂草，如看麦娘、日本看麦娘等。
本发明的环吡氟草酮一异丙胺盐B晶型，经测试，物理化学稳定性好，水溶性好，水中溶解度相比环吡氟草酮增大十余倍，相比环吡氟草酮钠盐增大约六倍，且B晶型或与其它有效成分的复配组合物，对小麦田禾本科杂草均有较好的防除效果，效果明显优于环吡氟草酮及其钠盐。
附图说明
图1是本发明中实施例2环吡氟草酮一异丙胺盐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 D8 advance，靶：Cu Kα(40kV，40mA)，样品到检测器距离：30cm，扫描范围：3°-45°(2θ值)，扫描步径：0.05s。
实施例1
参照CN 105218449 B方法制备得到环吡氟草酮原药，之后将1公斤环吡氟草酮与0.3公斤30％氢氧化钠水溶液反应，反应得到大量固体结晶，过滤固体并干燥，得到环吡氟草酮钠盐粉末。
实施例2
将实施例1所得1公斤环吡氟草酮与0.27公斤50％一异丙胺水溶液反应，反应得到大量固体结晶，过滤固体并干燥，得到环吡氟草酮一异丙胺盐粉末。
将1000克环吡氟草酮一异丙胺盐原药置于10L的烧瓶中，加入乙醇2L，加热搅拌至原料完全溶解，之后加入6升正庚烷或乙醚，使之析出大量结晶，过滤固体并干燥，得到环吡氟草酮一异丙胺盐B晶型粉末。
物理化学稳定性实验
将实施例1得到的环吡氟草酮及其钠盐和实施例2得到的环吡氟草酮一异丙胺B晶型三种粉末，经过HPLC实测环吡氟草酮含量为97.2％、环吡氟草酮钠盐含量为98.0％、环吡氟草酮一异丙胺B晶型含量均为98.0％，之后，将这三种原药粉末分别置于25℃、40℃、55℃和70℃烘箱里面，放置2个月进行热储实验，之后测试纯度，结果见下表1：
表1不同样品的稳定性考察
样品 环吡氟草酮 环吡氟草酮钠盐 环吡氟草酮一异丙胺盐B晶型
25℃ 97.2％ 98.0％ 98.0％
40℃ 96.6％ 97.8％ 97.9％
55℃ 96.1％ 97.3％ 97.5％
70℃ 95.5％ 96.6％ 97.1％
由表1可知，环吡氟草酮及其钠盐和环吡氟草酮一异丙胺盐B晶型在不同的温度条件下均有较好的稳定性，尤其在55℃和70℃较高温度下，B晶型依然保持良好的物理化学稳定性，纯度检测相当或略优于环吡氟草酮及其钠盐，具有很好的应用前景。
水中溶解度测定
将实施例1得到的环吡氟草酮及其钠盐和实施例2得到的环吡氟草酮一异丙胺盐B晶型三种粉末，均溶解在纯水中，在25℃下震荡24h，使之充分溶解，之后离心并过滤，滤液再过0.22μm滤膜，用HPLC测定水中溶解度，结果见下表2：
表2不同样品的水中溶解度测试结果
样品 纯水中溶解度(g/L)
环吡氟草酮 0.513
环吡氟草酮钠盐 1.053
环吡氟草酮一异丙胺盐B晶型 5.907
由表2结果可见，环吡氟草酮一异丙胺盐晶型B相对比环吡氟草酮及其钠盐，溶解度有明显的增加。
实施例1和实施例2制剂加工和大田药效实验
将实施例1得到的环吡氟草酮及其钠盐和实施例2得到的环吡氟草酮一异丙胺盐B晶型，按照相同的配方，加工成如下制剂，具体配方如下，其中有效成分A代表环吡氟草酮、环吡氟草酮钠盐和环吡氟草酮一异丙胺盐B晶型。
6％A OD
6％A+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.5％气相法白炭黑+5％150#溶剂油+油酸甲酯补足
14％A·吡氟酰草胺OD
6％A+8％吡氟酰草胺+5％十二烷基苯磺酸钙+8％脂肪醇聚氧乙烯醚+4％蓖麻油聚氧乙烯醚+2.0％有机膨润土+1.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
9％A·异恶唑草酮SC
6％A+3％异恶唑草酮+5％苯乙基苯酚聚氧乙烯醚磷酸酯一异丙胺盐+1.5％脂肪醇聚氧乙烯醚+0.2％黄原胶+2.2％硅酸镁铝+0.1％消泡剂+4％乙二醇+水补足
7.5％A·炔草酯OD
6％A+1.5％炔草酯+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.0％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
7.5％A·唑啉草酯OD
6％A+1.5％唑啉草酯+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.0％有机膨润土+2.0％气相法白炭黑+20％150#溶剂油+油酸甲酯补足
56％A·异丙隆WDG
6％A+50％异丙隆+5％十二烷基硫酸钠+8％聚羧酸盐分散剂+2％聚乙二醇4000+5.0％沉淀法白炭黑+高岭土补足
66％A·绿麦隆WDG
6％A+60％绿麦隆+5％十二烷基硫酸钠+8％聚羧酸盐分散剂+2％聚乙二醇4000+5.0％沉淀法白炭黑+高岭土补足
26％A·辛酰溴苯腈OD
6％A+20％辛酰溴苯腈+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
12％A·嗪草酮OD
6％A+6％嗪草酮+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.5％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
32.3％A·哒草特OD
2.3％A+30％哒草特+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.8％有机膨润土+2.5％气相法白炭黑+20％150#溶剂油+油酸甲酯补足
13％A·氨唑草酮OD
6％A+7％氨唑草酮+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.3％有机膨润土+2.0％气相法白炭黑+20％150#溶剂油+油酸甲酯补足
26％A·2甲4氯SL
6％A+20％2甲4氯+6％一异丙胺+40％乙醇+10％脂肪醇聚氧乙烯醚硫酸钠+水补足
11％A·氯氟吡氧乙酸OD
6％A+5％氯氟吡氧乙酸+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.3％有机膨润土+2.0％气相法白炭黑+12％150#溶剂油+油酸甲酯补足
6.5％A·氟氯吡啶酯OD
6％A+0.5％氟氯吡啶酯+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.3％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
18％A·麦草畏SL
6％A+12％麦草畏+7％一异丙胺+40％乙醇+10％脂肪醇聚氧乙烯醚硫酸钠+水补足
8.5％A·苯嘧磺草胺OD
6％A+2.5％苯嘧磺草胺+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
18％A·氟噻草胺OD
6％A+12％氟噻草胺+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.0％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
14％A·精异丙甲草胺OD
6％A+8％精异丙甲草胺+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
12％A·砜吡草唑OD
6％A+6％砜吡草唑+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
22％A·二甲戊灵OD
2％A+20％二甲戊灵+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.0％气相法白炭黑+20％150#溶剂油+油酸甲酯补足
6.6％A·甲基二磺隆OD
6％A+0.6％甲基二磺隆+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
8％A·氟唑磺隆OD
6％A+2％氟唑磺隆+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
6.6％A·啶磺草胺OD
6％A+0.6％啶磺草胺+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
43％A·苄草丹OD
3％A+40％苄草丹+5％十二烷基苯磺酸钙+5％脂肪醇聚氧乙烯醚+6％蓖麻油聚氧乙烯醚+2.5％有机膨润土+2.0％气相法白炭黑+10％150#溶剂油+油酸甲酯补足
大田效果试验：小麦3叶后，看麦娘3-4叶期、日本看麦娘3-4叶期，电动动喷雾器，兑水量30公斤/667m2，采用茎叶喷雾均匀喷雾，小区面积30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不同制剂防除小麦直播田杂草效果(％)——施药45d后防效
Figure BDA0001921102270000101
Figure BDA0001921102270000111
由表3可见，不同的环吡氟草酮制剂防除小麦直播田杂草效果相比，环吡氟草酮一异丙胺盐B晶型的防效明显高于环吡氟草酮及其钠盐制剂。
同时经过很多测试发现，本发明所述化合物及其组合物能防除很多关键禾本科杂草以及阔叶杂草。对不同施药方式下的小麦、玉米、水稻、甘蔗、大豆、棉花、油葵、马铃薯、果树、蔬菜等测试也显示出极好的选择性和商业价值。
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)

1.一种环吡氟草酮一异丙胺盐B晶型，其特征在于：X-射线粉末衍射谱图在衍射角2θ为6.8°、7.5°、8.1°、8.3°、10.1°、10.7°、11.3°、12.4°、13.7°、15.0°、16.4°、17.0°、17.8°、18.6°、19.1°、19.7°、20.5°、20.9°、21.8°、23.1°、24.1°、24.5°、25.1°、26.1°、27.3°、27.7°、28.3°、28.9°、29.6°、30.2°、31.0°、31.8°、32.5°、33.0°、33.5°、34.8°、35.2°、37.3°、38.2°、39.0°、39.6°、40.9°、41.3°、41.9°、42.8°、43.3°、43.9°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所述的一种环吡氟草酮一异丙胺盐B晶型，其特征在于：对应的I/I0分别为3.9、27.5、3.5、3.0、100.0、4.6、14.4、1.8、47.1、13.9、25.6、3.9、13.4、7.6、10.2、50.5、14.7、5.2、33.1、20.9、3.6、17.6、5.8、15.8、13.1、48.0、4.3、3.0、9.2、7.4、6.9、3.6、1.8、6.2、46.9、17.3、14.5、2.0、2.6、3.7、2.1、3.0、3.5、2.8、1.7、3.7、2.2。
3.根据权利要求1或2所述的一种环吡氟草酮一异丙胺盐B晶型，其特征在于：X射线粉末衍射图谱基本上如图1所示。
4.如权利要求1-3任意一项所述环吡氟草酮一异丙胺盐B晶型的制备方法，其特征在于：包括以下步骤：将环吡氟草酮一异丙胺盐溶解在乙醇中，搅拌至完全溶解，之后加入1-10倍体积的正庚烷或乙醚，使溶液析出大量固体结晶，所得固体结晶经干燥，得到环吡氟草酮一异丙胺盐B晶型。
5.一种除草复配组合物，其特征在于：包括(i)权利要求1-3任意一项所述环吡氟草酮一异丙胺盐B晶型；优选地，还包括(ii)一种或多种其他有效成分和/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。
6.根据权利要求5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吡氟酰草胺、异噁唑草酮、炔草酯、唑啉草酯、异丙隆、绿麦隆、辛酰溴苯腈、嗪草酮、哒草特、氨唑草酮、2甲4氯、氯氟吡氧乙酸、氟氯吡啶酯、麦草畏、苯嘧磺草胺、氟噻草胺、精异丙甲草胺、砜吡草唑、二甲戊灵、甲基二磺隆、氟唑磺隆、啶磺草胺、苄草丹及其衍生物中的一种或多种。
7.根据权利要求6所述的除草复配组合物，其特征在于，所述组合物中有效成分的总质量百分含量占总量的1-95％。
8.根据权利要求5-7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水悬浮剂、可分散油悬浮剂、乳油、微乳剂、颗粒剂、悬乳剂或水分散粒剂。
9.一种控制作物中杂草的方法，其特征在于，包括将除草有效量的权利要求1-3任意一项所述的环吡氟草酮一异丙胺盐B晶型或权利要求5-8任意一项所述的除草复配组合物使用在作物上或者杂草区域；优选地，所述作物为小麦，所述杂草为禾本科杂草(如看麦娘、日本看麦娘)。
10.如权利要求1-3任意一项所述的环吡氟草酮一异丙胺盐B晶型或权利要求5-8任意一项所述的除草复配组合物在控制杂草上的用途，优选地，将其用于防除有用作物中的杂草，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；优选地，所述作物为小麦，所述杂草为禾本科杂草(如看麦娘、日本看麦娘)。
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