CN105367557A - 一种环氧啉的制备方法 - Google Patents
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Abstract
本发明公开一种环氧啉的制备方法，属于杀虫剂制备技术领域。该方法首先在氮气保护下，将N-硝基亚氨基咪唑烷和有机溶剂加入到反应器中，然后分批加入氢化钠，加热至温度50～60℃，向反应器中慢慢滴加环氧氯丙烷，待反应产物冷却后，加入氯仿，用硅藻土过滤，再蒸发结晶析出，将处理后的滤液减压蒸馏得到淡黄色稠状固体，然后用热的氯仿萃取，最后用热的乙醇或丙酮重结晶得到环氧啉：1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺的纯品，产率约为83％。本发明方法反应时间更短、收率更高且绿色环保，更适合于大规模工业化生产。
Description
技术领域
本发明属于杀虫剂制备技术领域，具体涉及1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺即环氧啉的制备方法。
背景技术
环氧啉是基于计算机辅助药物分子设计(CADD)方法，即利用COMFA模拟结果，合成的4种新烟碱类化合物中杀虫效果最好的一种，其杀虫活性与全球市场销量最大的杀虫剂——吡虫啉的杀虫活性相当。但吡虫啉的广泛使用已使害虫产生了一定的抗药性，并且合成吡虫啉所用原料吡啶不但成本高，而且在生产过程中产生大量的污染物。而环氧啉不仅能有效地克服以上缺点，并且与吡虫啉一样具有较好的杀虫效果，且毒性更低，作为一种新化合物，具有选择性高、安全性好等特点，生产成本也仅为吡虫啉的三分之一，具有更加广阔的应用前景。2009年，中国专利CN101503406A公开了1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺的两种合成路线，路径1采用两步合成法，首先边搅拌边向乙二胺中滴加环氧氯丙烷，在温度为45℃左右，反应2～3h后减压蒸馏除去溶剂得到中间体环氧丙基乙二胺，然后将中间体和硝基胍溶于水中，边搅拌边滴加稀盐酸，于85℃左右反应2～3h后冷却，用二氯甲烷萃取，减压蒸馏除去溶剂，用丁酮重结晶，两步反应，反应温度较高，且后处理过程需使用大量的二氯甲烷等溶剂进行萃取，因此产品工业化价值不大。路线2先将N-硝基亚咪唑烷、碳酸钾及有机溶剂加入到反应瓶中，加热到80℃待反应物溶解后向其中滴加环氧氯丙烷，反应加热4h后结束，冷却到室温后，过滤，滤液蒸干，所得残留物加水，再用二氯甲烷萃取，减压蒸馏除去溶剂，再用丁酮重结晶，其后处理工艺较为繁琐，并且收率较低，限制了其工业化的生产应用。
发明内容
本发明针对现有技术存在的上述技术问题，提供一种环氧啉的制备方法。本发明采用N-硝基亚氨基咪唑烷和环氧氯丙烷为原料制备环氧啉：1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺。
本发明所提供一种环氧啉的制备方法的具体步骤如下：
(1)在氮气保护下，将N-硝基亚氨基咪唑烷和有机溶剂加入到反应器中，然后分批加入氢化钠，加热至温度50～60℃，待N-硝基亚氨基亚咪唑烷溶解后，向反应器中慢慢滴加环氧氯丙烷，滴加完毕，继续加热反应1～1.5h至反应结束，用TLC或HPLC监测反应进程。
所述环氧氯丙烷、N-硝基亚氨基咪唑烷及氢化钠的摩尔比为：环氧氯丙烷∶N-硝基亚氨基咪唑烷∶氢化钠＝1：1.1-1.5：1.1-1.5；所述有机溶剂为N,N'-二甲基甲酰胺或N,N'-二甲基甲酰胺与甲苯的混合溶剂；所述氢化钠的纯度为60wt％。
(2)待步骤(1)反应产物冷却后，向其中加入所述反应产物0.5倍体积的氯仿，进一步从有机溶剂中析出溶解的氯化钠副产物，用硅藻土过滤，除去滤液中氯化钠盐分，并通过水洗硅藻土以分离出氯化钠，再蒸发结晶析出。
(3)将经过步骤(2)处理后的滤液减压蒸馏除去大部分有机溶剂，得到淡黄色稠状固体，然后用热的氯仿萃取，再除去溶剂后得淡黄色固体产品，干燥后得环氧啉：1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺的粗品，减压蒸馏温度为40℃，压力为0.3Kpa。
(4)最后用热的乙醇或丙酮对步骤(3)得到的环氧啉：1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺粗品进行重结晶，最后制得所述环氧啉：1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺的纯品，产率约为83％。
其中：氢化钠分批加入，因为加入氢化钠会产生大量的氢气；抽滤时，使用硅藻土或白土可以较为彻底脱盐并分离出盐分副产品。
上述过程的反应式如下：
本发明具有以下技术特点：
1、采用氢化钠可以有效的将N-硝基亚氨基咪唑烷中共振式中酸性较弱的氢完全解离并转为钠盐，且不会产生其他有机副产物。
2、使用极性和溶解性更强的N,N'-二甲基甲酰胺为反应溶剂，可以大大减少溶剂的使用量，而且减压蒸馏出的N,N'-二甲基甲酰胺可以循环套用，更加经济环保。
3、反应温度为50～60℃，热条件更加温和，能耗更少。
4、产物分离过程中可有效分离出副产品氯化钠，以减少固体废弃物的产生。
5、氯仿在反应后续处理过程中也可以循环利用，减少成本。
6、相比现有技术，本发明方法反应时间更短，收率更高，且后处理工艺也相对简单。
总之，本发明方法是制备环氧啉的一种比较绿色环保的工艺方法，具有更高的实用价值，更适合于大规模工业化生产。
附图说明
图1为本发明制备环氧啉的工艺流程图。
具体实施方式
实施例1：将97.5g(0.75mol)N-硝基亚氨基咪唑烷、18g(0.75mol)氢化钠及125mLN,N'-二甲基甲酰胺和75mL甲苯溶剂加入到反应瓶中，加热到65℃，待咪唑烷基本溶解后，向其中滴加46.3g(0.5mol)环氧氯丙烷，滴加完毕后继续反应1.5h，并用TLC或HPLC跟踪监测反应进程直至反应结束。反应结束后，待反应物冷却，加入100mL氯仿，通过硅藻土过滤除盐后过滤，再将滤液减压蒸馏除去大部分溶剂，得到稠状固体，用热的氯仿萃取，收集萃取液，除去氯仿得到淡黄色固体产品，干燥得粗品，用热的乙醇溶液重结晶，干燥得浅黄色的1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺固体产品77.3g，收率83.2％，熔点：87～90℃。
实施例2：将97.5g(0.75mol)N-硝基亚氨基咪唑烷、18g(0.75mol)氢化钠和175mLN,N'-二甲基甲酰胺溶剂加入到反应瓶中，加热到60℃，待N-硝基亚氨基咪唑烷基本溶解后，向其中滴加46.3g(0.5mol)环氧氯丙烷，滴加完毕后继续反应2h，TLC或HPLC监测反应进程。反应结束后，待反应物冷却后，过滤，将滤液进行减压蒸馏去除大部分N,N'-二甲基甲酰胺，得粘稠状固体，加***多次洗涤，过滤，得到浅黄色固体，粗品再用热的丙酮重结晶，干燥得浅黄色的1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺固体78g，收率83.9％，熔点：87～90℃。
Claims (1)
1.一种环氧啉的制备方法，其特征在于该制备方法的具体步骤如下：
(1)在氮气保护下，将N-硝基亚氨基咪唑烷和有机溶剂加入到反应器中，然后分批加入氢化钠，加热至温度50～60℃，待N-硝基亚氨基亚咪唑烷溶解后，向反应器中慢慢滴加环氧氯丙烷，滴加完毕，继续加热反应1～1.5h至反应结束，用TLC或HPLC监测反应进程；所述环氧氯丙烷、N-硝基亚氨基咪唑烷及氢化钠的摩尔比为：环氧氯丙烷∶N-硝基亚氨基咪唑烷∶氢化钠＝1：1.1-1.5：1.1-1.5；所述有机溶剂为N,N'-二甲基甲酰胺或N,N'-二甲基甲酰胺与甲苯的混合溶剂；所述氢化钠的纯度为60wt％；
(2)待步骤(1)反应产物冷却后，向其中加入所述反应产物0.5倍体积的氯仿，进一步从有机溶剂中析出溶解的氯化钠副产物，用硅藻土过滤，除去滤液中氯化钠盐分，并通过水洗硅藻土以分离出氯化钠，再蒸发结晶析出；
(3)将经过步骤(2)处理后的滤液减压蒸馏除去大部分有机溶剂，得到淡黄色稠状固体，然后用热的氯仿萃取，再除去溶剂后得淡黄色固体产品，干燥后得环氧啉：1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺的粗品，减压蒸馏温度为40℃，压力为0.3KPa；
(4)最后用热的乙醇或丙酮对步骤(3)得到的环氧啉：1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺粗品进行重结晶，最后制得所述环氧啉：1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺的纯品。
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| 卢伦，等: "吡虫啉衍生物的合成", 《合成化学》 * |
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