CN107987104A - 草甘膦除草离子液体及其制备和应用 - Google Patents

草甘膦除草离子液体及其制备和应用 Download PDF

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CN107987104A
CN107987104A CN201711327923.8A CN201711327923A CN107987104A CN 107987104 A CN107987104 A CN 107987104A CN 201711327923 A CN201711327923 A CN 201711327923A CN 107987104 A CN107987104 A CN 107987104A
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ion liquid
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俞建忠
何红梅
张昌朋
许振岚
吴珉
张春荣
何开雨
朱亚红
俞瑞鲜
赵华
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Zhejiang Academy of Agricultural Sciences
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Abstract

本发明提供一种具有除草活性的新型草甘膦离子液体类化合物，其化学式为

Description

草甘膦除草离子液体及其制备和应用
技术领域
本发明属于农用除草剂领域，特别是涉及草甘膦除草离子液体类化合物及其制备和应用。
背景技术：
草甘膦(glyphosate)，又名镇草宁、农达(Roundup)等，其化学名称为：N-(膦酰基甲基)甘氨酸，是1971年由美国孟山都公司开发的一种有机磷除草剂。草甘膦是目前世界上最经济的内吸传导非选择性除草剂，其主要通过茎叶吸收，传导至地下部分，抑制植物体内烯醇丙酮基莽草素膦酸合成酶，从而抑制植物体内莽草素向苯丙氨酸、酪氨酸及色氨酸转化，是蛋白质合成受到干扰，导致杂草死亡。
离子液体是由阴、阳离子构成的熔点低于100℃的盐(许多在室温呈液态)。离子液体具有几乎无蒸气压、高的热稳定性和化学稳定性、优良的溶解性能、优异的电化学特性及易回收、可设计等优点，其绝大多数的应用研究都集中在溶剂、催化和新材料方面。近几年来离子液体的物理化学属性、生物学性质备受关注。由于离子液体的活性可以通过离子液体的可设计性进行调节，而且许多常见离子液体的结构或组分和活性药物成分的前驱体相似，人们开始认识到它可能具有潜在的生物活性。
最近许多学者纷纷致力于离子液体应用于药物及农用化学品的研究。国外Pernak首次(ACS Sustainable Chem.Eng.,2014,2,2845-2851)报道了草甘膦除草离子液体，对此类离子液体化合物的除草活性进行了初步探索，新型草甘膦除草离子液体由于阳离子的引入，改变草甘膦理化性质的同时，明显提高了草甘膦除草的活性。草甘膦除草剂作为全球第一大农药，对其开展增效改性研究，对控制农药使用量，减少对环境危害显的尤为重要。
发明内容：
本发明目的是提供一种具有除草活性的新型草甘膦离子液体类化合物和这些新化合物的制备方法以及这些化合物在制备除草剂中的用途。通过生物活性测定试验，研究者发现，草甘膦离子液体化合物由于不同阳离子的引入可以调控草甘膦的活性，部分新化合物表现出优异的除草活性。
本发明的技术方案如下：
式(I)所示的草甘膦离子液体类化合物：
式(I)中：R1、R2、R3、R4为C1-C16烷基的季铵阳离子；或R1为C1-C16烷基、R2为氢或烷氧基的哌啶阳离子；或R1为甲基、R2为C1-C4烷基的吡咯阳离子；或R1为C1-C16烷基的吡啶阳离子；或R1为甲基、R2为C1-C9烷氧(硫)基的咪唑阳离子；
进一步，优选所述式(I)中所示的阳离子选自下列之一：N-三甲基-N-十六烷基铵阳离子、N-二甲基-N-二烯丙基铵阳离子、N-二甲基哌啶阳离子、N-甲基-N-癸基哌啶阳离子、N-十六烷基吡啶阳离子、N-甲基吡啶阳离子、N-甲基-N-丁基吡咯阳离子、1-甲基-3-辛氧甲基咪唑阳离子、1-甲基-3-辛硫甲基咪唑阳离子、1-甲基-3-丁基咪唑阳离子。
本发明所述的式(I)化合物可由如下方法制得：将式(II)化合物和溶剂混合，在碱性物质的作用下，0～60℃(优选50℃)搅拌反应，待反应液澄清后，加入式(III)化合物，继续搅拌反应0.5～1小时(优选1小时)，加入二氯甲烷萃取，取有机相真空减压浓缩，并在真空干燥箱中干燥，获得式(I)所示的草甘膦离子液体类化合物；
本发明所述溶剂为蒸馏水、甲醇、乙腈或丙酮中的一种或多种，优选为蒸馏水；
本发明所述碱性物质为碳酸钾、氢氧化钠、氢氧化钾或氢化钠中的一种或多种，优选为氢氧化钠；
本发明所述式(II)化合物与式(III)化合物和碱性物质的量之比为1.0:1.0:1.0～1.5，优选为1.0:1.0:1.1。
本发明所述有机溶剂体积用量以式(II)化合物的物质的量计为1-10mL/mmol，优选为2mL/mmol；
与现有技术相比，本发明的有益效果主要体现在：本发明提供了一种草甘膦离子液体类化合物的制备方法及应用，该化合物为具有除草活性的新化合物，为新农药的研发提供了基础。
具体实施方式
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此：
实施例1
草甘膦-N-三甲基-N-十六烷基铵盐的制备。
向50mL圆底烧瓶中加入草甘膦1.69g(10mmol)、蒸馏水(20mL)和10％的NaOH水溶液(10mmol)，50℃下磁力搅拌，待反应液澄清后，加入十六烷基三甲基氯化铵3.2g(10mmol)，室温下搅拌反应1小时。
加入二氯甲烷(3×20mL)萃取，萃取完成后，有机相用饱和食盐水洗一次，蒸馏水洗一次，旋转蒸发，并在真空干燥箱中干燥得到黄色油状液体，收率98％。
1H NMR(CDCl3,400MHz):4.03(s,2H),3.28(s,2H),3.20(t,J＝8.5Hz,2H),3.13(s,9H),2.83(s,J＝12.0Hz,2H),1.59(q,J＝7.3Hz,2H),1.26(m,26H),0.88(t,J＝6.7Hz,3H)。
实施例2
草甘膦-N-二甲基-N-二烯丙基铵盐的制备。
向250mL圆底烧瓶中加入草甘膦1.69g(10mmol)、甲醇(100mL)和氢化钠0.36g(15mmol)，0℃下磁力搅拌，待反应液澄清后，加入二烯丙基二甲基氯化铵1.62g(10mmol)，室温下搅拌反应0.5小时。
加入二氯甲烷(3×20mL)萃取，萃取完成后，有机相用饱和食盐水洗一次，蒸馏水洗一次，旋转蒸发，并在真空干燥箱中干燥得到黄色油状液体，收率90％。
1H NMR(CDCl3,400MHz):6.00(m,2H),5.70(m,2H),5.63(m,2H),4.00(s,2H),3.84(d,J＝7.1Hz,4H),3.43(s,2H),3.10(s,J＝12.0Hz,2H),2.98(s,6H)。
实施例3
草甘膦-N-二甲基哌啶盐的制备。
向50mL圆底烧瓶中加入草甘膦1.69g(10mmol)、乙腈(10mL)和碳酸钾1.52g(11mmol)，30℃下磁力搅拌，待反应液澄清后，加入1-二甲基哌啶鎓氯化物3.2g(10mmol)，室温下搅拌反应1小时。
加入二氯甲烷(3×20mL)萃取，萃取完成后，有机相用饱和食盐水洗一次，蒸馏水洗一次，旋转蒸发，并在真空干燥箱中干燥得到黄色液体，收率82％。
1H NMR(DMSO-d6,400MHz):5.70(s,2H),3.96(s,2H),3.33(t,J＝5.8Hz,4H),3.18(s,J＝11.5Hz,2H),3.07(s,6H),1.73(q,J＝5.2Hz,4H),1.48(q,J＝5.9Hz,2H)。
实施例4
草甘膦-N-甲基-N-癸基哌啶盐的制备。
向100mL圆底烧瓶中加入草甘膦1.69g(10mmol)、丙酮(50mL)和氢氧化钾0.73g(13mmol)，60℃下磁力搅拌，待反应液澄清后，加入N-葵基-N-甲基哌啶溴盐3.18g(10mmol)，室温下搅拌反应1小时。
加入二氯甲烷(3×20mL)萃取，萃取完成后，有机相用饱和食盐水洗一次，蒸馏水洗一次，旋转蒸发，并在真空干燥箱中干燥得到黄色油状液体，收率95％。
1H NMR(CDCl3,400MHz):5.88(s,2H),3.90(s,2H),3.42(s,3H),3.29(m,6H),3.18(s,J＝12.4Hz,2H),1.77(m,4H),1.62(m,2H),1.53(m,2H),1.23(m,14H),0.86(t,J＝5.2Hz,3H)。
实施例5
草甘膦-N-十六烷基吡啶盐的制备。
向50mL圆底烧瓶中加入草甘膦1.69g(10mmol)、甲醇(20mL)和氢氧化钾0.62g(11mmol)，40℃下磁力搅拌，待反应液澄清后，加入溴代十六烷基吡啶3.84g(10mmol)，室温下搅拌反应0.5小时。
加入二氯甲烷(3×20mL)萃取，萃取完成后，有机相用饱和食盐水洗一次，蒸馏水洗一次，旋转蒸发，并在真空干燥箱中干燥得到黄色油状液体，收率99％。
1H NMR(CDCl3,400MHz):9.01(d,J＝5.5Hz,2H),8.42(t,J＝7.8Hz,1H),8.02(t,J＝7.1Hz,2H),6.86(d,J＝9.1Hz,1H),4.90(s,2H),4.65(t,J＝7.4Hz,2H),3.76(s,2H),3.30(s,J＝10.8Hz,2H),1.86(q,J＝7.2Hz,2H),1.25(26H,m),0.87(t,J＝6.7Hz,3H)。
实施例6
草甘膦-N-甲基吡啶盐的制备。
向50mL圆底烧瓶中加入草甘膦1.69g(10mmol)、蒸馏水(20mL)和氢氧化钾0.56g(10mmol)，50℃下磁力搅拌，待反应液澄清后，加入溴代甲基吡啶1.74g(10mmol)，室温下搅拌反应1小时。
加入二氯甲烷(3×20mL)萃取，萃取完成后，有机相用饱和食盐水洗一次，蒸馏水洗一次，旋转蒸发，并在真空干燥箱中干燥得到浅黄色粘稠状固体，收率99％。
1H NMR(CDCl3,400MHz):9.24(s,1H),8.96(d,J＝6.0Hz,1H),8.82(d,J＝8.2Hz,1H),8.14(t,J＝7.3Hz,1H),4.88(s,2H),4.49(s,3H),3.52(s,2H),3.05(s,J＝11.0Hz,2H)。
实施例7
草甘膦-N-甲基-N-丁基吡咯盐的制备。
向50mL圆底烧瓶中加入草甘膦1.69g(10mmol)、蒸馏水(20mL)和10％的NaOH水溶液(15mmol)，30℃下磁力搅拌，待反应液澄清后，加入1-甲基-1-丁基溴化吡咯烷2.22g(10mmol)，室温下搅拌反应1小时。
加入二氯甲烷(3×20mL)萃取，萃取完成后，有机相用饱和食盐水洗一次，蒸馏水洗一次，旋转蒸发，并在真空干燥箱中干燥得到黄色液体，收率99％。
1H NMR(DMSO-d6,400MHz):4.76(s,2H),3.55(s,2H),3.47(m,4H),3.30(t,J＝8.4Hz,2H),2.98(s,3H),2.85(s,J＝12.0Hz,2H),2.07(m,4H),1.66(q,J＝4.1Hz,2H),1.30(m,J＝7.4Hz,2H),0.92(t,J＝7.3Hz,3H)。
实施例8
草甘膦-1-甲基-3-辛氧甲基咪唑盐的制备。
向50mL圆底烧瓶中加入草甘膦1.69g(10mmol)、蒸馏水(30mL)和10％的NaOH水溶液(13mmol)，40℃下磁力搅拌，待反应液澄清后，加入1-甲基-3-辛氧甲基碘化咪唑鎓3.52g(10mmol)，室温下搅拌反应1小时。
加入二氯甲烷(3×20mL)萃取，萃取完成后，有机相用饱和食盐水洗一次，蒸馏水洗一次，旋转蒸发，并在真空干燥箱中干燥得到黄色油状液体，收率96％。
1H NMR(CDCl3,400MHz):10.05(t,J＝1.1Hz,1H),7.44(t,J＝1.9Hz,1H),7.39(t,J＝1.2Hz,1H),6.02(s,2H),5.54(s,2H),4.78(s,2H),4.19(s,3H),3.40(t,J＝6.5Hz,2H),2.83(s,J＝10.5Hz,2H),1.48(q,J＝6.3Hz,2H),1.22(m,10H),0.87(t,J＝6.9Hz,3H)。
实施例9
草甘膦-1-甲基-3-辛硫甲基咪唑盐的制备。
向50mL圆底烧瓶中加入草甘膦1.69g(10mmol)、甲醇(20mL)和氢氧化钾0.62g(11mmol)，40℃下磁力搅拌，待反应液澄清后，加入1-甲基-3-辛硫甲基碘化咪唑鎓3.68g(10mmol)，室温下搅拌反应1小时。
加入二氯甲烷(3×20mL)萃取，萃取完成后，有机相用饱和食盐水洗一次，蒸馏水洗一次，旋转蒸发，并在真空干燥箱中干燥得到黄色油状液体，收率91％。
1H NMR(CDCl3,400MHz):10.19(t,J＝1.1Hz,1H),7.50(t,J＝1.8Hz,1H),7.38(t,J＝1.8Hz,1H),6.12(s,2H),5.33(s,2H),4.75(s,2H),3.90(s,3H),2.88(s,J＝10.5Hz,2H),2.52(t,J＝7.3Hz,2H),1.49(q,J＝7.3Hz,2H),1.23(m,10H),0.87(t,J＝6.8Hz,3H)。
实施例10
草甘膦-1-丁基-3-甲基咪唑盐的制备。
向100mL圆底烧瓶中加入草甘膦1.69g(10mmol)、甲醇(40mL)和氢氧化钾0.62g(11mmol)，50℃下磁力搅拌，待反应液澄清后，加入1-丁基-3-甲基碘化咪唑鎓2.66g(10mmol)，室温下搅拌反应0.75小时。
加入二氯甲烷(3×20mL)萃取，萃取完成后，有机相用饱和食盐水洗一次，蒸馏水洗一次，旋转蒸发，并在真空干燥箱中干燥得到黄色油状液体，收率90％。
1H NMR(DMSO-d6,400MHz):10.05(t,J＝1.1Hz,1H),7.90(t,J＝1.9Hz,1H),7.84(t,J＝1.9Hz,1H),6.00(s,2H),4.66(s,2H),4.28(t,J＝7.1Hz,2H),3.95(s,3H),2.85(s,J＝11.0Hz,2H),1.87(q,J＝7.4Hz,2H),1.38(d,J＝7.4Hz,2H),0.98(t,J＝7.3Hz,3H)。
除草活性测试
化合物的配置：用分析天平(0.0001g)称取一定质量的原药，用含1％吐温-80乳化剂的DMF溶解配制成1.0～5.0％母液，然后用蒸馏水稀释备用。供试靶标为稗草、马唐、反枝苋、马齿苋和鸭拓草，取内径6cm花盆，装复合土(菜园土：育苗基质，1：2，v/v)至3/4处，直接播种上述五种杂草靶标(芽率≥85％)，覆土0.5cm，待杂草长至3叶期左右备用。各化合物按照600g a.i./ha剂量在自动喷雾塔施药后，待杂草叶面药液晾干后移入温室培养。21天后调查结，计算鲜重减少百分率，结果见表1。
表1该系列10个新化合物室内除草活性试验结果(鲜重防除效果％)
从上表中可以看出，10个新化合物对稗草、马唐、反枝苋、马齿苋和鸭拓草等杂草均有一定的效果，部分除草活性比市售除草剂农达的除草效果更好。

Claims (10)

1.一种草甘膦除草离子液体化合物，其特征在于，其结构式如(I)所示：
式(I)中：R1、R2、R3、R4为C1-C16烷基的季铵阳离子；或R1为C1-C16烷基、R2为氢或烷氧基的哌啶阳离子；或R1为甲基、R2为C1-C4烷基的吡咯阳离子；或R1为C1-C16烷基的吡啶阳离子；或R1为甲基、R2为C1-C9烷氧(硫)基的咪唑阳离子。
2.如权利要求1所述的草甘膦除草离子液体化合物，其特征在于，所述式(I)中的季铵阳离子选自N-三甲基-N-十六烷基铵阳离子或N-二甲基-N-二烯丙基铵阳离子。
3.如权利要求1所述的草甘膦除草离子液体化合物，其特征在于，所述式(I)中的哌啶阳离子选自N-二甲基哌啶阳离子或N-甲基-N-癸基哌啶阳离子。
4.如权利要求1所述的草甘膦除草离子液体化合物，其特征在于，所述式(I)中的吡咯阳离子选自N-十六烷基吡啶阳离子、N-甲基吡啶阳离子或N-甲基-N-丁基吡咯阳离子。
5.如权利要求1所述的草甘膦除草离子液体化合物，其特征在于，所述式(I)中的咪唑阳离子选自1-甲基-3-辛氧甲基咪唑阳离子、1-甲基-3-辛硫甲基咪唑阳离子或1-甲基-3-丁基咪唑阳离子。
6.一种制备草甘膦除草离子液体化合物的方法，其用于制备权利要求1-5中任一项所述的化合物，具体包括如下步骤：
将式(II)化合物和溶剂混合，在碱性物质的作用下，0～60℃(优选50℃)搅拌反应，待反应液澄清后，加入式(III)化合物，继续搅拌反应0.5～1小时(优选1小时)，加入二氯甲烷萃取，取有机相真空减压浓缩，并在70℃真空干燥箱中干燥24小时，获得式(I)所示的草甘膦离子液体类化合物；
7.如权利要求6所述的一种制备草甘膦除草离子液体化合物的方法，其特征在于，所述溶剂为蒸馏水、甲醇、乙腈或丙酮中的一种或多种，优选为蒸馏水。
8.如权利要求6所述的一种制备草甘膦除草离子液体化合物的方法，其特征在于，所述碱性物质为碳酸钾、碳酸氢钠、氢氧化钠、氢氧化钾或氢化钠中的一种或多种，优选为氢氧化钠。
9.如权利要求6所述的一种制备草甘膦除草离子液体化合物的方法，其特征在于，所述式(II)化合物与式(III)化合物和碱性物质的量之比为1.0:1.0:1.0～1.5，优选为1.0:1.0:1.1；
所述有机溶剂体积用量以式(II)化合物的物质的量计为1-10mL/mmol，优选为2mL/mmol。
10.如权利要求1-5所述的草甘膦离子液体化合物应用于制备除草剂。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110003270A (zh) * 2019-03-29 2019-07-12 浙江省农业科学院 一种草甘膦双阳离子型离子液体化合物及其制备方法和应用
CN113735797A (zh) * 2021-10-11 2021-12-03 天津博创工程科技有限公司 一种用于萃取精馏提纯草酸二甲酯的萃取剂、其制备方法及草酸二甲酯的纯化方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0124351A1 (en) * 1983-05-02 1984-11-07 Stauffer Chemical Company Mixed long-chain alkylammonium salts of N-phosphonomethylglycine
CN101621925A (zh) * 2007-02-26 2010-01-06 陶氏益农公司 衍生自羧酸除草剂和一些三烷基胺或杂芳基胺的离子液体
WO2012006313A2 (en) * 2010-07-06 2012-01-12 The Board Of Trustees Of The University Of Alabama Herbicidal compositions and methods of use

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0124351A1 (en) * 1983-05-02 1984-11-07 Stauffer Chemical Company Mixed long-chain alkylammonium salts of N-phosphonomethylglycine
CN101621925A (zh) * 2007-02-26 2010-01-06 陶氏益农公司 衍生自羧酸除草剂和一些三烷基胺或杂芳基胺的离子液体
WO2012006313A2 (en) * 2010-07-06 2012-01-12 The Board Of Trustees Of The University Of Alabama Herbicidal compositions and methods of use

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110003270A (zh) * 2019-03-29 2019-07-12 浙江省农业科学院 一种草甘膦双阳离子型离子液体化合物及其制备方法和应用
CN110003270B (zh) * 2019-03-29 2021-09-28 浙江省农业科学院 一种草甘膦双阳离子型离子液体化合物及其制备方法和应用
CN113735797A (zh) * 2021-10-11 2021-12-03 天津博创工程科技有限公司 一种用于萃取精馏提纯草酸二甲酯的萃取剂、其制备方法及草酸二甲酯的纯化方法

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