CN107298645B - 一种制备2, 2’-二硝基联苄的方法 - Google Patents
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Abstract
本发明公开一种采用催化方法制备2,2’‑二硝基联苄的方法及这种制备方法所使用的催化剂制备方法。本发明的2,2’‑二硝基联苄制备方法是：使用邻硝基氯苄为原料，以氯代甲烷为溶剂，加入胺类牺牲剂，以贵金属金负载于纳米二氧化钛载体为催化剂，在光照射下进行反应，反应前充分超声分散，反应过程中溶剂回流，反应过程中反应体系进行搅拌保持悬浮状态，反应完成后固液分离后得到偶联产物2,2’‑二硝基联苄。本发明的制备方法极大地降低了传统工艺中高温所导致的能耗，避免了多步骤多次提纯带来的成本提升和产物损失，而且在生产中产生的三废少，工艺简洁，产品收率较高，符合绿色化学概念。
Description
技术领域
本发明涉及一种化合物的制备方法，特别是一种用于抗癫痫药物卡马西平的中间体的制备方法，确切讲本发明涉及一种采用催化方法制备2,2’-二硝基联苄的方法。
背景技术
癫痫是一种慢性神经疾病，发病年龄跨度很大，即从新生儿阶段到老年均有可能发病。癫痫的病程长，有很高的不可预知性和突然性，严重影响患者日常生活和工作，患者及家属往往承受巨大的心理压力，是世界卫生组织重点防控的精神疾病之一。根据国家卫生部和中国抗癫痫协会的联合调查，我国癫痫患病率约7‰，活动性癫痫患病率约4.6‰。所以抗癫痫药物的研究作为该领域的一个热点研究方向，具有巨大的社会意义。
卡马西平作为早已应用于临床的一种广谱抗癫痫药，对复杂局限性发作疗效较好，对强直痉挛性发作和单纯局限性发作也有很好疗效。而且对于外周神经痛疗效优于苯妥英钠，也可用于治疗躁狂症。
在目前主流的卡马西平合成路线中，2,2’-二硝基联苄为其关键中间体，其合成方法直接影响该药品的毒副反应、生产成本和市场售价。目前该中间体的生产方法有以下几种：
一、申请公布号CN 105753709A的中国发明专利公开的一种2,2’二硝基联苄的制备方法，该方法采用了三步法，首先将邻硝基甲苯和邻硝基苯甲醛与离子液体和氢氧化钾混合偶联，生成1,2-二（2-硝基苯基）乙醇；再用三溴化磷进行溴代反应，生成1,2-二（2-硝基苯基）溴乙烷；最后使用硼氢化钠脱溴，得到目标产物。由于该方法步骤繁琐，需要反复提纯中间产物，而且生产出的卡马西平不可避免地有溴化物残留，患者服用后产生的毒副反应远大于无溴工艺产品，因而对产品的品质和售价产生较大的不利影响，工业化应用受限。
二、《中国医药工业杂志》，第33卷，第11期，525-526《10,11-二氢-5H-二苯并[b,f]氮杂的合成》公开了使用邻硝基甲苯为原料，以石油醚为溶剂，使用甲酸乙酯和甲醇钠，制备出目标产物。该方法为目前无溴法制备2,2’-二硝基联苄的主流方法，其具有反应条件温和。但是这一方法存在的不足是：其产品纯度较低，并且生产过程耗水量巨大，三废处理难度大、耗能高，不符合绿色化学的概念。
因此，寻找一种绿色高效环保的制备2,2-二氨基联苄的方法迫在眉睫。
发明内容
在本发明提供一种可克服现有技术不足的，催化法制备2,2’-二硝基联苄的方法。
本发明的制备2,2’-二硝基联苄的方法是：使用邻硝基氯苄为原料，以氯代甲烷为溶剂，加入胺类牺牲剂，以贵金属金负载于纳米二氧化钛载体为催化剂，在光照射下进行反应，反应前充分超声分散，反应过程中溶剂回流，反应过程中反应体系进行搅拌保持悬浮状态，反应完成后固液分离后得到偶联产物2,2’-二硝基联苄。
优先地，本发明的制备2,2’-二硝基联苄的方法所使用的催化剂为负载型纳米金催化剂，催化剂用量为邻硝基氯苄用量质量比的5～25%，反应时光照射的波长为340～800nm。
优选地，本发明的制备2,2’-二硝基联苄的方法在反应时光照射的波长为350～450nm。
本发明的实验表明，在光照射下进行反应时采用二氯甲烷或四氯化碳为溶剂效果最好，而且在反应时溶剂浓度过浓存在原料的浪费，转化率上不去，但浓度过稀则会造成溶剂浪费，因此本发明推荐溶剂使用量控制在为邻硝基氯苄质量的50～300倍为宜，优先地的为邻硝基氯苄质量的150倍。
本发明的制备2,2’-二硝基联苄的方法所使用的催化剂的制备方法为：将氯金酸甲醇溶液与纳米二氧化钛混合并充分搅拌均匀，水冷条件下用高压汞灯照射6h，待原浅黄色悬浊液转变为紫色后，离心分离，以水和乙醇清洗至中性，再进行干燥处理，金纳米颗粒粒径为3～30nm。
本发明的催化剂还可采用下述方法制备：将纳米二氧化钛和氯金酸水溶液，搅拌均匀，放置于超声中30min，置于机械搅拌上，中速搅拌，同时在其中缓慢加入硼氢化钠水溶液，待完全加入后关闭机械搅拌，静置过夜，再离心分离，以水清洗至中性，再进行干燥处理，所形成金纳米颗粒粒径为3～30nm。
本发明建议采用P25材料，负载于其上的金纳米颗粒粒径控制在5~20nm为好。
上述两种催化剂的制备方法中，使用光照法制备的催化剂其附着的金纳米颗粒粒径小，分散性好，但是负载率低，一般在3%以下，而采用硼氢化钠制备时催化剂负载率较高，可以达到10%以上，但是粒径稍大。在催化剂用于制备2,2’-二硝基联苄时相同活性物质质量下催化反应，以用光照法制备的催化剂活性较高。
优先地，本发明的催化剂制备方法中所用的二氧化钛为P25。
本发明的这种光催化制备2,2’-二硝基联苄的方法，极大的降低了传统工艺中高温导致的能耗，在生产中采用一锅法，避免了多步骤多次提纯带来的成本提升和产物损失，而且在生产中产生的三废少，工艺简洁，产品收率较高，符合绿色化学概念，特别适合工业化生产。本发明催化剂制备方法简单、廉价，所得到的产物且经洗涤可反复使用。
具体实施方式
本发明以下通过具体的实例进行详细说明。
实施例一
A．负载型纳米金催化剂的制备
取250ml烧瓶，加入200mg P25和5ml 0.01mol/L的氯金酸水溶液，搅拌均匀，放置于超声中30min，置于机械搅拌上，中速搅拌。取100ml 0.01mol/L的硼氢化钠水溶液，用注射泵以30ml/h的速度慢速加入到氯金酸P25混合液之中。待完全加入后关闭机械搅拌，静置过夜，离心分离，以水清洗至中性，放入烘箱干燥备用。
B．2,2-二硝基联苄的制备
取容量为5ml石英烧瓶，加入5mg负载型金纳米催化剂，20mg邻硝基氯苄，30mg二异丙基乙胺，3ml二氯甲烷，超声分散，打开卤素灯，反应7h。离心分离催化剂，收集反应产物。液相经GCMS检测，目标产物2,2’-二硝基联苄占55%，催化剂经水洗、乙醇清洗后烘干，可重复使用。
实施例二
A．负载型纳米金催化剂的制备
取10ml石英水冷反应管，加入200mg P25和5ml 0.01mol/L的氯金酸甲醇溶液，搅拌均匀，水冷条件下经由高压汞灯照射6h，原浅黄色悬浊液转变为紫色，离心分离，以水和乙醇清洗至中性，放入烘箱干燥备用。
B．2,2-二硝基联苄的制备
取容量为5ml石英烧瓶，加入5mg负载型金纳米催化剂，20mg邻硝基氯苄，28mg二异丙基乙胺，3ml四氯化碳，超声分散，打开高压汞灯，反应5h。离心分离催化剂，收集反应产物。液相经GCMS检测，目标产物2,2’-二硝基联苄占61%，催化剂经水洗、乙醇清洗后烘干，可重复使用。
以上所述，仅为本发明的最佳实施例，并非用来限定本发明保护的范围，本发明所要求保护的范围以权利要求书记载的内容为准。
Claims (1)
1.一种制备2,2’-二硝基联苄的方法，其特征在于：
A．负载型纳米金催化剂的制备：取10ml石英水冷反应管，加入200mg P25和5ml0.01mol/L的氯金酸甲醇溶液，搅拌均匀，水冷条件下经由高压汞灯照射6h，原浅黄色悬浊液转变为紫色，离心分离，以水和乙醇清洗至中性，放入烘箱干燥备用；
B．2,2’ -二硝基联苄的制备：取容量为5ml石英烧瓶，加入5mg负载型纳米金催化剂，20mg邻硝基氯苄，28mg二异丙基乙胺，3ml四氯化碳，超声分散，打开高压汞灯，反应5h；离心分离催化剂，收集反应产物。
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