CN105481839A - 一种光活性环氧啉对映体的制备方法 - Google Patents

一种光活性环氧啉对映体的制备方法 Download PDF

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CN105481839A
CN105481839A CN201510822732.3A CN201510822732A CN105481839A CN 105481839 A CN105481839 A CN 105481839A CN 201510822732 A CN201510822732 A CN 201510822732A CN 105481839 A CN105481839 A CN 105481839A
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nitroimidazoline
base amine
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CN105481839B (zh
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张千峰
夏佳美
徐文芳
范芳芳
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ANHUI QIANHE NEW MATERIAL TECHNOLOGY DEVELOPMENT Co Ltd
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Abstract

本发明公开一种光活性环氧啉对映体的制备方法，属于光学活性药物不对称催化合成技术领域。该方法首先合成1-烯丙基-N-硝基亚咪唑烷-2-基胺，然后再合成1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺对映体。本发明方法采用氢化钠可以有效地将N-硝基亚氨基咪唑烷共振式中酸性较弱的氢完全除去并转化为钠盐，且不会产生有机副产物；通过不对称环氧化，能够以较高的产率分别得到左旋或右旋的对映体产品；本发明能够得到高纯度的对映体产品，大大提高产品的杀虫活性，减少对环境的污染。

Description

一种光活性环氧啉对映体的制备方法
技术领域
本发明属于光学活性药物不对称催化合成技术领域，具体涉及1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺(即环氧啉)对映体的制备方法。
背景技术
环氧啉是在普通杀虫剂吡虫啉基础上发展起来的一种高效，低毒杀虫剂，目前已在黄瓜、棉花等农作物中逐步推广，是代替有机磷、有机氯杀虫剂的最佳品种。但是目前主要的合成与生产工艺所得到的是环氧啉的消旋体产品(见中国专利CN101503406A)，如果能将这对消旋体拆分为左旋(-)和右旋(+)产品，那么这对具有光学活性对映体产品的药用效果一定会更好，但是工业上拆分消旋体的成本很高，且难以实现产业化的推广；为此，本发明设计采用氯丙稀与N-硝基亚氨基咪唑烷合成1-烯丙基-N-硝基亚咪唑烷-2-基氨，再通过Sharpless不对称环氧化将其氧化成1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺(即环氧啉)的具有光学活性对映体产物。
Sharpless不对称环氧化的最大优点在于：反应试剂均为商业化，且廉价易得，而其环氧化产物的收率通常具有超过90％的e.e.值(对映体含量)，另外还可以根据反应模型预测产物的手性。具有光学活性的手性化合物在医药、农药、材料、香料和食品等领域有着重要的应用，而且光学活性的手性化合物其价值要远远高于其外消旋体产物，环氧啉产品作为可以分离和转化的手性化合物，有必要研究其左旋(-)和右旋(+)对映体的合成与分离及药理性质及杀虫活性，以及可能存在毒性或环境污染等问题。
发明内容
本发明针对上述现有技术存在的问题，提供1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺(即环氧啉)对映体的制备方法。
本发明所述光活性环氧啉对映体，即1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺对映体的结构式为：
本发明所提供的光活性环氧啉对映体：1-(2,3-环氧丙基)-N-硝基亚咪唑烷-2-基胺的制备方法具体步骤如下：
(1)合成1-烯丙基-N-硝基亚咪唑烷-2-基胺：
在氮气保护下，将N-硝基亚氨基咪唑烷与有机溶剂加入到反应器中，待N-硝基亚氨基咪唑烷基本溶解后，在搅拌下向反应器中分批加入氢化钠，加完氢化钠后继续搅拌30分钟，再向反应器中缓慢滴加氯丙烯，滴加完毕后，于温度35-40℃条件下搅拌反应，并用TLC或HPLC监测反应进程，直至反应结束；冷却后减压蒸馏出有机溶剂，得橙黄色油状液体，加所述橙黄色油状液体等体积的乙醚于温度-10℃下析出淡黄色晶状固体，趁冷过滤，得粗产品，用氯仿重结晶，得到1-烯丙基-N-硝基亚咪唑烷-2-基胺的纯品。
所述有机溶剂为DMF(N,N'-二甲基甲酰胺)或DMF与甲苯的混合溶剂，所述氯丙烯∶N-硝基亚氨基咪唑烷∶氢化钠的摩尔比为：1：1.1-1.5：1.1-1.5；所述氢化钠的纯度为60wt％；所述减压蒸馏温度为40℃,压力为0.3KPa；整个反应溶液体系中可加入少量的分子筛。
(2)合成1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺对映体：
在氮气保护下，向反应器中加入一定量的有机溶剂氯仿，于-10-O℃温度下，先后向其中加入四异丙基氧钛Ti(Oi-Pr)4、L(+)-酒石酸二乙酯((+)DET)或L(-)-酒石酸二乙酯((-)DET)，搅拌15分钟后加入步骤(1)制备的1-烯丙基-N-硝基亚咪唑烷-2-基胺，最后加入氧化剂间氯过氧苯甲酸(M-CPBA)，将反应所得的均相溶液搅拌12h，期间用TLC或HPLC监测反应的产物转化进程，除去溶剂后，用石油醚洗涤，可得粗产品，经氯仿-石油醚混合溶剂重结晶得到1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺对映体的纯品。
所述四异丙基氧钛：L(+)-酒石酸二乙酯：1-烯丙基-N-硝基亚咪唑烷-2-基胺：间氯过氧苯甲酸的摩尔比为1:1:1:2；所述氯仿-石油醚的体积比为2:1；整个反应溶液体系中可加入少量的分子筛。
其中：步骤(1)中合成1-烯丙基-N-硝基亚咪唑烷-2-基胺的反应温度为35-40℃，温度高会导致未反应的氯丙烯挥发掉，影响1-烯丙基-N-硝基亚咪唑烷-2-基胺的产量；所用氢化钠纯度为60wt％，氢化钠分批缓慢加入，以避免在加入的过程中会产生大量氢气的逸出；步骤(2)中的Sharpless不对称环氧化反应为-10℃-0℃(可用冰盐浴调制)。
上述制备过程的反应式如下：
本发明与现有技术相比具有以下技术特点：
(1)采用氢化钠可以有效地将N-硝基亚氨基咪唑烷共振式中酸性较弱的氢可完全除去，并可以转化为钠盐，且不会产生有机副产物.
(2)第一步烯丙基产物的制备反应温度为35-40℃，热条件较为温和，能耗少，同时还可以避免1-烯丙基-N-硝基亚咪唑烷-2-基胺产物的自聚现象.
(3)通过Sharpless不对称环氧化，能够以较高的产率分别得到左旋或右旋的对映体产品，且所需要的环氧化催化剂价格便宜并易于得到.
(4)能够得到高纯度的对映体产品，大大提高产品的杀虫活性，也会相应地降低农药在实际应用中的使用量，减少对环境的污染。
具体实施方式
实施例1：本发明提供的1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺对映体具体制备方法如下：
(1)：1-烯丙基-N-硝基亚咪唑烷-2-基胺的制备：
在氮气保护下，将6.5g(0.05mol)的N-硝基亚胺基咪唑烷加入到50mL的N,N'-二甲基甲酰胺中，搅拌30分钟使之完全溶解后，将2.4g氢化钠分3-5次加入其中，继续搅拌约1h，得到均相的浅黄色溶液。将4.9mL(0.06mol)氯丙烯用恒压滴加漏斗缓慢滴加到上述溶液中，滴加完毕后再缓慢升温到40℃，TLC或HPLC方法用以监测反应过程，直至反应进行完全。通过硅藻土抽滤，除去反应过程中产生的无机盐，得黄色透明溶液，40℃下减压蒸馏(压力:0.3KPa)N,N'-二甲基甲酰胺溶剂，再加等体积的无水乙醚在-10℃下可析出淡黄色晶状固体，趁冷过滤，得到粗产品，用氯仿重结晶，即可得到1-烯丙基-N-硝基亚咪唑烷-2-基胺的纯品，收率：82％，m.p.:67-89℃。1HNMR(CDCl3,400MHz，ppm):δ2.69(s,2H,NCH2CH2N),2.85(s,2H,NCH2CH2N),3.16(s,2H,NCH2CH＝),3.16(s,2H,NCH2CH＝),5.09-5.23(dd,J＝6.6Hz,2H,NCH2CH＝CH2),5.94(d,J＝6.4Hz,1H,NCH2CH＝CH2),8.22(s,1H,NH).MS(ESI):m/z170.17[M+],124.16[M+-NO2].Anal.Calc.forC6H10N4O2:C,42.35；H,5.92；N,32.92％.Found:C,42.17；H,5.89；N,32.77％。
(2)分别制备L(-)-1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺以及D(+)-1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺：
L(-)-1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺的制备：
将20mL的氯仿加入到100mL的三颈圆底烧瓶中，在-10℃(冰盐浴)下搅拌冷却，先后分别加入0.297mL(1mmol)的四异丙基氧钛，0.172mL(0.206g，1mmol)的L(-)-酒石酸二乙酯，搅拌约10分钟，溶液呈均相后，再加入0.17g(1mmol)1-烯丙基-N-硝基亚咪唑烷-2-亚胺，最后一次加入0.345g(2mmol)间氯过氧苯甲酸；所得均相溶液在冰箱于-10-0℃下搅拌约12h，反应期间可通过TLC或HPLC方法监测环氧化转化过程，待反应物全部转为产物后，除去反应溶剂，用石油醚洗涤得浅黄色固体粉末，再用氯仿-石油醚(2:1)重结晶，得纯品，收率：77％，ee值：90％,m.p.:97～99℃。1HNMR(CDCl3,400MHz，ppm):δ2.52(s,2H,CH2-OCH-CH2),2.69(s,2H,CH2-OCH-CH2),2.78(d,1H,J＝6.1Hz,CH2-OCH-CH2),2.81(s,2H,NCH2CH2N),2.89(s,2H,NCH2CH2N),8.14(s,1H,NH).MS(ESI):m/z188.17[M+],140.16[M+-NO2].Anal.Calc.forC6H10N4O3:C,38.71；H,5.41；N,30.09％.Found:C,38.64；H,5.37；N,30.04％。
D(+)-1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺的制备：
将20mL的氯仿加入到100mL的三颈圆底烧瓶中，在-10℃(冰盐浴)下搅拌冷却，先后分别加入0.297mL(1mmol)的四异丙基氧钛，0.172mL(0.206g，1mmol)的D(+)-酒石酸二乙酯，搅拌10分钟，溶液呈均相后，再加入0.17g(1mmol)1-烯丙基-N-硝基亚咪唑烷-2-亚胺，最后一次加入0.345g(2mmol)间氯过氧苯甲酸；所得均相溶液在冰箱于-10-0℃下搅拌约12h，反应期间可通过TLC或HPLC方法监测环氧化转化过程，待反应物全部转为产物后，除去反应溶剂，用石油醚洗涤得浅黄色固体粉末，再用氯仿-石油醚(2:1)重结晶，得纯品，收率：81％，ee值：93％,m.p.:96～97℃。1HNMR(CDCl3,400MHz，ppm):δ2.54(s,2H,CH2-OCH-CH2),2.67(s,2H,CH2-OCH-CH2),2.79(d,1H,J＝6.1Hz,CH2-OCH-CH2),2.84(s,2H,NCH2CH2N),2.91(s,2H,NCH2CH2N),8.17(s,1H,NH).MS(ESI):m/z188.17[M+],140.16[M+-NO2].Anal.Calc.forC6H10N4O3:C,38.71；H,5.41；N,30.09％.Found:C,38.69；H,5.36；N,30.02％。

Claims (1)

1.一种光活性环氧啉对映体的制备方法，其特征在于该制备方法具体步骤如下：
(1)合成1-烯丙基-N-硝基亚咪唑烷-2-基胺：
在氮气保护下，将N-硝基亚氨基咪唑烷与有机溶剂加入到反应器中，待N-硝基亚氨基咪唑烷基本溶解后，在搅拌下向反应器中分批加入氢化钠，加完氢化钠后继续搅拌30分钟，再向反应器中缓慢滴加氯丙烯，滴加完毕后，于温度35-40℃条件下搅拌反应，并用TLC或HPLC监测反应进程，直至反应结束；冷却后减压蒸馏出有机溶剂，得橙黄色油状液体，加所述橙黄色油状液体等体积的乙醚于温度-10℃下析出淡黄色晶状固体，趁冷过滤，得粗产品，用氯仿重结晶，得到1-烯丙基-N-硝基亚咪唑烷-2-基胺的纯品；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，所述氯丙烯∶N-硝基亚氨基咪唑烷∶氢化钠的摩尔比为：1:1.1-1.5:1.1-1.5；所述氢化钠的纯度为60wt％；所述减压蒸馏温度为40℃,压力为0.3KPa；
(2)合成1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺对映体：
在氮气保护下，向反应器中加入一定量的有机溶剂氯仿，于-10-O℃温度下，先后向反应器加入四异丙基氧钛Ti(Oi-Pr)4、L(+)-酒石酸二乙酯或L(-)-酒石酸二乙酯，搅拌15分钟后加入步骤(1)制得的1-烯丙基-N-硝基亚咪唑烷-2-基胺，最后加入氧化剂间氯过氧苯甲酸，将反应所得的均相溶液搅拌12h，期间用TLC或HPLC监测反应的产物转化进程，除去溶剂后，用石油醚洗涤，可得粗产品，经氯仿-石油醚混合溶剂重结晶得到1-(1,2-环氧丙基)-N-硝基亚咪唑烷-2-基胺对映体的纯品；所述四异丙基氧钛：L(+)-酒石酸二乙酯：1-烯丙基-N-硝基亚咪唑烷-2-基胺：间氯过氧苯甲酸的摩尔比为1:1:1:2；所述氯仿-石油醚的体积比为2:1。
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