CN106831618B - 一种季铵盐类化合物及其应用 - Google Patents

一种季铵盐类化合物及其应用 Download PDF

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CN106831618B
CN106831618B CN201510882228.2A CN201510882228A CN106831618B CN 106831618 B CN106831618 B CN 106831618B CN 201510882228 A CN201510882228 A CN 201510882228A CN 106831618 B CN106831618 B CN 106831618B
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程学明
梁爽
马宏娟
侯岳华
崔东亮
刘鹏飞
李斌
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Abstract

本发明属于除草剂领域。具体地说是一种季铵盐类化合物及其应用。化合物如通式(I)所示：

Description

一种季铵盐类化合物及其应用
技术领域
本发明属于除草剂领域。具体地说是一种季铵盐类化合物及其应用。
背景技术
由于杂草种群的演替、变迁以及对化学农药抗药性的产生和迅速发展，人们对生态环境保护意识的不断加强，对化学农药污染、农药对非靶标生物影响的认识以及在农药生态环境中归宿问题的重视不断提高。随着世界耕地面积的逐渐减少、人口的不断增长及对粮食需求量的增加，迫使人们迅速发展农业生产技术、改进完善耕作制度，并需要不断发明新型的和改进的除草化合物和组合物。
季铵盐型化合物具有良好的脂溶性及水溶性，并且一些化合物也被报道具有除草活性。如JP54088229报道了某些2,4-D类季铵盐型化合物可作为除草剂，例如其中的1号化合物KC：
本发明在化合物KC结构基础上进行改造修饰，如在其苯环上引入饱和或不饱和芳杂环取代基，以期发现更优活性的化合物。
本发明所涉及一种季铵盐类化合物及其制备和除草活性未见公开。
发明内容
本发明的目的是提供一种结构新颖的季铵盐类化合物及其应用。
为实现上述目的，本发明采用技术方案为：
一种季铵盐类化合物，结构式如下，
式中：
M选自H、F或Cl；
n选自0-10；
R1选自C1-C12烷基、C1-C12卤代烷基或苯基，其中，R1选自苯基时苯环上的氢可以被一个或多个如下基团取代：卤素、硝基、CN、C1-C6烷基或C1-C6卤代烷基；
R2选自C1-C12烷基、C1-C12卤代烷基或苯基，其中，R2选自苯基时苯环上的氢可以被一个或多个如下基团取代：卤素、硝基、CN、C1-C6烷基或C1-C6卤代烷基；
或者R1和R2同所连接的氮一起形成：
R3选自C1-C12烷基；
Y-选自氟离子、氯离子、溴离子、碘离子、醋酸根、对甲苯磺酸根或硫酸氢根；
X选自NH、O或S；
Q选自如下结构：
本发明中较优选的化合物为：通式I中：
式中：
M选自H、F或Cl；
n选自1、2、3或4；
R1选自C1-C4烷基、C1-C4卤代烷基或苯基，其中，R1选自苯基时苯环上的氢可以被一个或多个如下基团取代：卤素、硝基、CN、C1-C6烷基或C1-C6卤代烷基；
R2选自C1-C4烷基、C1-C4卤代烷基或苯基，其中，R2选自苯基时苯环上的氢可以被一个或多个如下基团取代：卤素、硝基、CN、C1-C6烷基或C1-C6卤代烷基；
或者R1和R2同所连接的氮一起形成：
R3选自C1-C4烷基；
Y-选自氟离子、氯离子、溴离子或碘离子；
X选自NH或O；
Q选自Q21、Q31、Q42、Q47或Q61。
本发明中进一步优选的化合物为：通式I中
式中：
M选自F
n选自1；
R1选自甲基或乙基；
R2选自甲基或乙基；
R3选自甲基；
Y-选自碘离子；
X选自NH或O；
Q选自Q31或Q61。
本发明中再进一步优选的化合物为：通式I中
式中：
M选自F
n选自1；
R1选自甲基；
R2选自甲基；
R3选自甲基；
Y-选自碘离子；
X选自NH或O；
Q选自Q61。
本发明通式I化合物可由如下方法制备，反应式中除另有注明的外其他各基团的定义同前：
通式I化合物可由通式II化合物与通式III化合物在适宜的溶剂中，温度为-10℃到沸点之间反应0.5-48小时制得。适宜的溶剂选自氯仿，二氯甲烷，四氯化碳，正己烷，苯，甲苯，乙酸乙酯，THF或二氧六环等。R3Y有市售，如碘甲烷等。
通式化合物II制备方法如下：
通式化合物(IV)与酰卤化试剂于适宜的溶剂，温度为-10℃到沸点之间反应0.5-48小时制得中间体酰氯V。适宜的酰卤化试剂选自草酰氯、氯化亚砜、三氯化磷、三溴化磷、五氯化磷或五溴化磷。适宜的溶剂选自氯仿、二氯甲烷、四氯化碳、正己烷、苯、甲苯、乙酸乙酯、THF或二氧六环等。
中间体酰氯V再与通式VI化合物在适宜的溶剂中，温度为-10℃到沸点之间反应0.5-48小时制得产物II。适宜的溶剂选自氯仿、二氯甲烷、四氯化碳、正己烷、苯、甲苯、乙酸乙酯、THF或二氧六环等。加入适宜的碱性物质，如吡啶、三乙胺、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾或碳酸氢钾等对反应有利。
通式VI化合物有市售。
通式化合物IV制备方法如下：
通式化合物VII溶于适宜的溶剂中，并加入碱性水溶液，温度为-10℃到沸点之间反应0.5-48小时，制得化合物III。适宜的溶剂选自氯仿、二氯甲烷、四氯化碳、正己烷、苯、甲苯、乙酸乙酯、甲醇、乙醇、THF或二氧六环等；适宜的碱选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾或碳酸氢钠等。通式化合物VII有市售。
部分通式I化合物的结构和物理性质见表1
表1
本发明的通式I化合物具有除草活性，可用于农业上防治多种杂草。如：在苗后使用可有效控制杂草。本发明的季铵盐类化合物具有优异的除草活性。因此本发明的技术方案还包括通式(I)化合物用于控制杂草的用途。
本发明还包括以通式I化合物为活性组分的除草组合物。该除草组合物中活性组分的重量百分含量为5-90％。该除草组合物中还包括农业上可接受的载体。
本发明的除草组合物可以多种制剂的形式施用。通常将本发明的化合物溶解或分散于载体中配制成制剂以便作为除草剂使用时更易于分散。例如：这些化学制剂可被制成可湿性粉剂或乳油等。因此，在这些组合物中，至少加入一种液体或固体载体，并且通常需要加入适当的表面活性剂。
本发明还提供了防治杂草的实施方法，该方法包括将除草有效量的本发明的除草组合物施于所述杂草或所述杂草生长的场所或其生长介质的表面上。较为适宜有效剂量为每公顷1克到1000克，优选有效剂量为每公顷10克到500克。对于某些应用，可在本发明的除草组合物中加入一种或多种其它的除草剂，由此可产生附加的优点和效果。
本发明的化合物既可以单独使用也可以和其它已知的杀虫剂、杀菌剂、植物生长调节剂或肥料等一起混合使用。
应明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动。
以该类化合物为活性组分的除草组合物，以满足农业生产迅速发展的需要。。
具体实施方式
下列实施例和生测试验结果可用来进一步说明本发明，但不意味着限制本发明。
实施例1、化合物25的合成：
(1)中间体羧酸(IV-1)的制备
向250毫升的反应瓶中加入唑酮草酯(10.30克，25毫摩尔)和80毫升四氢呋喃，搅拌至全溶，冷却下加入氢氧化钠(1.00克，25毫摩尔)和水(100毫升)形成的溶液，自然升至室温搅拌反应5小时，停止反应，加入100毫升乙酸乙酯萃取，水相用浓盐酸酸化，过滤，滤饼干燥得7.68克中间体酸IV-1。
(2)中间体(II-1)的合成
向反应瓶中加入中间体酸IV-1(0.5克，1.3毫摩尔)，搅拌下滴加氯化亚砜20毫升，加毕，加热回流，搅拌反应，反应3小时。反应接近完全，减压蒸去过量的氯化亚砜，将得到的产物用二氯甲烷30毫升溶解，缓慢滴加入N,N-二甲基-2-羟基乙胺(0.12克，1.3毫摩尔)，室温搅拌反应，TLC(乙酸乙酯﹕石油醚＝1﹕1)监测，待反应完成后，减压除去二氯甲烷，残余物经过柱色谱(乙酸乙酯﹕石油醚＝1﹕2作洗脱剂，青岛海洋生物化工厂分厂生产的100～140目硅胶)得淡黄色液体(II-1)0.45克。
化合物(II-1)1H NMR(300MHz,CDCl3)δ(ppm):7.47(d,1H),7.30(d,1H),7.05(t,1H),4.59(t,1H),4.30-4.25(m,2H),3.55-3.24(m,1H),2.59-2.55(m,2H),2.48(s,3H),2.26(s,6H)。
(3)产物(25)合成
向反应瓶中加入中间体II-1(0.3克，0.66毫摩尔)、5毫升乙醇，待样品溶解后，再加入乙醚30毫升，搅拌下滴加碘甲烷(0.47克，3.29毫摩尔)，室温搅拌，反应大约30分钟，出现白色固体，将反应混合物过滤，无水乙醚洗，得白色固体0.22克(25)。
化合物(II-1)1H NMR(300MHz,CDCl3)δ(ppm):7.49(d,1H),7.33(d,1H),7.07(t,1H),4.72-4.63(m,3H),4.19-4.12(m,2H),3.58-3.36(m,11H),2.48(s,3H)1.65(s,3H),1.20(t,1H)。
实施例2、化合物27的合成：
(1)中间体(II-2)的合成
向反应瓶中加入中间体酸IV-1(0.5克，1.3毫摩尔)，搅拌下滴加氯化亚砜20毫升，加毕，加热回流，搅拌反应，反应3小时。反应接近完全，减压蒸去过量的氯化亚砜，将得到的产物用二氯甲烷30毫升溶解，缓慢滴加入N,N-二甲基-2-氨基乙胺(0.12克，1.3毫摩尔)，室温搅拌反应，TLC(乙酸乙酯﹕石油醚＝1﹕1)监测，待反应完成后，减压除去二氯甲烷，残余物经过柱色谱(乙酸乙酯﹕石油醚＝1﹕1作洗脱剂，青岛海洋生物化工厂分厂生产的100～140目硅胶)得淡黄色液体(II-2)0.47g。
化合物(II-1)1H NMR(300MHz,CDCl3)δ(ppm):7.47(d,1H),7.30(d,1H),7.04(t,1H),4.58-4.54(m,1H),3.76-3.70(m,1H),3.58-3.33(m,2H),3.22-3.14(m,1H),2.47(s,3H),2.45-2.41(m,2H),2.23(s,6H)。
(2)产物(27)合成
向反应瓶中加入中间体II-2(0.3克，0.66毫摩尔)、5毫升乙醇，待样品溶解后，再加入乙醚30毫升，搅拌下滴加碘甲烷(0.47克，3.29毫摩尔)，室温搅拌，反应大约30分钟，出现白色固体，将反应混合物过滤，无水乙醚洗，得白色固体0.3克(27)。
化合物(27)1H NMR(300MHz,CDCl3)δ(ppm):8.48(s,1H),7.51(d,1H),7.32(d,1H),7.02(t,1H),4.71(t,1H),3.78-3.76(m,3H),3.57-3.47(m,2H),3.32(s,9H),2.48(s,3H),1.68(s,3H),1.21(t,1H)。
表1其它化合物均可用此方法合成。
实施例3、化合物KC的合成：
(1)中间体II-1的合成
将2-(2,4-二氯苯氧)乙酸(1.00克，4.52毫摩尔)加入反应瓶中，搅拌下滴加氯化亚砜(5.38克，45.24毫摩尔)，加毕，加热回流，搅拌反应，反应3小时。反应接近完全，减压蒸去过量的氯化亚砜，将得到的产物用20毫升二氯甲烷溶解，加入2毫升三乙胺，缓慢滴加到2-二甲氨基乙醇(2.02克，22.62毫摩尔)中，室温搅拌反应，TLC(乙酸乙酯﹕石油醚＝1﹕1，加1％(V/V)三乙胺)监测，反应约6小时。待反应完成后，减压蒸除二氯甲烷，残余物柱色谱(乙酸乙酯﹕石油醚＝1﹕2作洗脱剂，加1％(V/V)三乙胺，青岛海洋生物化工厂分厂生产的100～140目硅胶)纯化得II-1，淡黄色油状液体0.94克，HPLC归一纯度95％。
(2)化合物KC的合成
将II-1(0.70克，2.40毫摩尔)用20毫升乙醚溶解后加入反应瓶中，搅拌下滴加碘甲烷(2.04克，13.38毫摩尔)，TLC(乙酸乙酯﹕石油醚＝1﹕2，加1％(V/V)三乙胺)监测。室温搅拌，约10分钟后溶液变浑浊，继续搅拌6小时。过滤，滤饼用无水乙醚洗涤，石油醚洗涤，得白色固体0.60克，m.p.125-126℃。
化合物KC：(300MHz,D2O)δ8.33(s,1H),7.52(s,1H),7.30(d,1H),6.97(d,1H),4.71(s,2H),3.77(s,2H),3.50(t,2H),3.14(s,9H)。
生测实例
实施例3：除草活性的测定
采用对作用机制敏感的盆栽法中的茎叶处理对本发明的化合物分别进行了初步活性测试。
将定量的禾本科杂草(稗草，金色狗尾草)种子分别播于直径为7cm的装有营养土的纸杯中，播后覆土1cm，镇压、淋水后在温室按常规方法培养。禾本科杂草长至2～3叶期，按试验设计剂量，在履带式作物喷雾机(英国Engineer Research Ltd.设计生产)上进行茎叶喷雾处理(喷雾压力1.95kg/cm2，喷液量500L/hm2，履带速度1.48km/h)。试验设3次重复。试材处理后置于操作大厅，待药液自然阴干后，放于温室内按常规方法管理，观察并记录杂草对药剂的反应情况，处理后定期目测调查供试药剂对杂草的防除效果。
通式I化合物对苘麻、百日草具有高防效，其中化合物25、27在600g a.i./hm2剂量下对苘麻的防效达98％，化合物25、27在600g a.i./hm2剂量下对百日草的防效达100％。
选取通式I中部分化合物，进行了对苘麻、百日草的活性比较试验，结果见表2、表3。
表2：通式I中部分化合物对苘麻的活性
注：KC是JP54088229专利中1号化合物，其制备见合成实施例6。
表3：通式I中部分化合物对百日草的活性
注：“/”代表未测 。

Claims (7)

1.一种季铵盐类化合物，如通式I所示：
式中：
M选自F；
n选自1；
R1选自C1-C12烷基；
R2选自C1-C12烷基；
R3选自C1-C12烷基；
Y-选自碘离子；
X选自O；
Q为
2.如权利要求1所述的化合物，其特征在于，通式I中：
式中：
M选自F；
n选自1；
R1选自C1-C4烷基；
R2选自C1-C4烷基；
R3选自C1-C4烷基；
Y-选自碘离子；
X选自O；
Q为
3.如权利要求2所述的化合物，其特征在于，通式I中：
式中：
M选自F
n选自1；
R1选自甲基或乙基；
R2选自甲基或乙基；
R3选自甲基；
Y-为碘离子；
X为O；
Q为
4.如权利要求1所述的化合物，其特征在于，通式I中：
式中：
M选自F
n选自1；
R1选自甲基；
R2选自甲基；
R3选自甲基；
Y-为碘离子；
X为O；
Q为
5.权利要求1所述的通式(I)化合物用于控制杂草的应用。
6.一种除草组合物，含有如权利要求1所述的作为活性组分的通式(I)化合物和农业上可接受的载体，组合物中活性组分的重量百分含量为5-90％。
7.一种控制杂草的方法，其特征在于：向杂草、杂草的生长介质或地点上施用除草有效剂量的如权利要求6所述的除草组合物。
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