CN103819395B - 一种制备2-碘-5-苯基吡啶的方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明提供一种制备2-碘-5-苯基吡啶的方法，涉及2-碘-5-苯基吡啶工业生产技术领域，选用2-氯-5-苯基吡啶为初始原料，在催化剂和配体存在的条件下，与无机碘盐进行卤素置换反应，经过简单后处理即可得到高纯度、高产率的2-碘-5-苯基吡啶。本发明采用的方法非高温高压反应，工艺安全稳定，适于大规模生产；所用原料对生产设备无腐蚀性，且所用溶剂均可回收重复利用，符合绿色化学的理念，降低了环境污染的危害，并且节约了生产成本；产物纯度与收率均较高，能有效提高生产企业的收益。
Description
技术领域
本发明涉及2-碘-5-苯基吡啶工业生产技术领域，具体涉及一种制备2-碘-5-苯基吡啶的方法。
背景技术
2-碘-5-苯基吡啶是制备海洋生物碱ClathryimineB的重要原料，ClathryimineB是一种新发现的印度洋珊瑚Clathryabasilana的提取物[TetrahedronLetters,Vol.37,1996,p2389-2390]，其结构十分新颖，不同于一般的多肽和萜类化合物，目前世界范围内关于ClathryimineB的生物活性研究刚刚开始。因此，开发一种简单、高效、环境友好的2-碘-5-苯基吡啶合成工艺，对研究ClathryimineB具有十分重要的前瞻性意义。
现阶段，制备2-碘-5-苯基吡啶的方法主要有以下几种：
1、美国专利US4971982(1990)以2-氯-5-苯基吡啶为原料，在高碘酸水溶液中加热制备2-碘-5-苯基吡啶。该方法用到大量高碘酸溶液，对生产设备有一定腐蚀，且产生大量废酸，无法重复利用，不符合绿色化学理念，且生产成本昂贵，不适于大规模生产。
2、以2-氨基-5-苯基吡啶为原料，用亚硝基叔丁酯，碘等，在溶剂中通过桑德迈尔反应制备2-碘-5-苯基吡啶[MonatsheftefurChemie,Vol.134,p573-583]。该方法文献摩尔收率只有45%，且用到大量碘，成本昂贵，不适于生产。
发明内容
本发明所要解决的技术问题在于提供一种制备2-碘-5-苯基吡啶的方法，该方法产物收率较高，成本低廉，工艺条件稳定，操作简单，适用于规模化生产，为制备2-碘-5-苯基吡啶提供了一种新的思路和方法。
本发明所要解决的技术问题采用以下技术方案来实现：
一种制备2-碘-5-苯基吡啶的方法，其特征在于，选用2-氯-5-苯基吡啶为初始原料，在催化剂和配体存在的条件下，与无机碘盐进行卤素置换反应，经过简单后处理即可得到高纯度、高产率的2-碘-5-苯基吡啶；
反应过程的具体制备步骤如下：
（1）卤素置换：氮气保护下，将2-氯-5-苯基吡啶与催化剂和配体，无机碘盐，反应溶剂混合，加热反应至无原料2-氯-5-苯基吡啶剩余，降温进行后处理；
（2）后处理：减压蒸馏回收反应溶剂，加提取溶剂提取反应产物，抽滤分离不溶物，浓缩提取溶剂得到产物2-碘-5-苯基吡啶粗品，用重结晶方法纯化得到纯品产物。
进一步地，步骤（1）所用催化剂为卤化亚铜盐，配体包括1,10-菲罗啉、1,2-环己二胺和N,N'-二甲基-1,2-环己二胺，无机碘盐为碘化钠或碘化钾，反应溶剂包括二甲基亚砜、N,N-二甲基甲酰胺和N-甲基吡咯烷酮，反应温度为100至200℃；步骤（2）中提取溶剂包括四氢呋喃、甲苯、乙酸乙酯和1,2-二氯乙烷，重结晶溶剂包括甲醇、乙醇和异丙醇。
进一步地，步骤（1）所用催化剂为溴化亚铜或碘化亚铜，配体包括1,2-环己二胺和N,N'-二甲基-1,2-环己二胺，无机碘盐为碘化钠或碘化钾，反应溶剂包括N,N-二甲基甲酰胺和N-甲基吡咯烷酮，反应温度为100至200℃；步骤（2）中提取溶剂包括乙酸乙酯和1,2-二氯乙烷，重结晶溶剂包括甲醇和乙醇。
进一步地，步骤（1）所用催化剂为碘化亚铜，配体为N,N'-二甲基-1,2-环己二胺，无机碘盐为碘化钾，反应溶剂为N-甲基吡咯烷酮，反应温度为180℃；步骤（2）中提取溶剂为1,2-二氯乙烷，重结晶溶剂为乙醇。
本发明制备2-碘-5-苯基吡啶的方法，所得产物纯度与收率均较高，工艺条件稳定，操作简单，适用于规模化生产。
本发明的有益效果是：
1、本专利采用的方法非高温高压反应，工艺安全稳定，适于大规模生产；
2、本专利采用的方法，所用原料对生产设备无腐蚀性，且所用溶剂均可回收重复利用，符合绿色化学的理念，降低了环境污染的危害，并且节约了生产成本；
3、本专利采用的制备2-碘-5-苯基吡啶的方法，产物纯度与收率均较高，能有效提高生产企业的收益。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明，但下述实施例仅仅为本发明的优选实施例，并非全部。基于实施方式中的实施例，本领域技术人员在没有做出创造性劳动的前提下所获得其它实施例，都属于本发明的保护范围。
实施例1：
10升玻璃反应器配机械搅拌，温度计，在氮气保护下加入原料2-氯-5-苯基吡啶500g，一定量的碘化亚铜和1,10-菲罗啉，相对于原料2-氯-5-苯基吡啶1.1摩尔当量的碘化钠，3升二甲基亚砜作为溶剂，加热至160℃反应，当体系内无原料2-氯-5-苯基吡啶剩余时停止反应，降至室温，减压蒸馏回收溶剂二甲基亚砜，以便下次套用，向反应器内剩余物中加入2升四氢呋喃，搅拌半小时，抽滤，滤液浓缩干，得到产物2-碘-5-苯基吡啶粗品，向产物粗品中加入一定量的甲醇，进行重结晶，得到产物纯品，摩尔收率为66%。
实施例2：
10升玻璃反应器配机械搅拌，温度计，在氮气保护下加入原料2-氯-5-苯基吡啶500g，一定量的碘化亚铜和1,2-环己二胺，相对于原料2-氯-5-苯基吡啶1.1摩尔当量的碘化钾，3升N,N-二甲基甲酰胺作为溶剂，加热至150℃反应，当体系内无原料2-氯-5-苯基吡啶剩余时停止反应，降至室温，减压蒸馏回收溶剂N,N-二甲基甲酰胺，以便下次套用，向反应器内剩余物中加入2升乙酸乙酯，搅拌半小时，抽滤，滤液浓缩干，得到产物2-碘-5-苯基吡啶粗品，向产物粗品中加入一定量的乙醇，进行重结晶，得到产物纯品，摩尔收率为76%。
实施例3：
10升玻璃反应器配机械搅拌，温度计，在氮气保护下加入原料2-氯-5-苯基吡啶500g，一定量的碘化亚铜和N,N'-二甲基-1,2-环己二胺，相对于原料2-氯-5-苯基吡啶1.1摩尔当量的碘化钾，3升N-甲基吡咯烷酮作为溶剂，加热至150℃反应，当体系内无原料2-氯-5-苯基吡啶剩余时停止反应，降至室温，减压蒸馏回收溶剂N-甲基吡咯烷酮，以便下次套用，向反应器内剩余物中加入2升1,2-二氯乙烷，搅拌半小时，抽滤，滤液浓缩干，得到产物2-碘-5-苯基吡啶粗品，向产物粗品中加入一定量的乙醇，进行重结晶，得到产物纯品，摩尔收率为79%。
实施例4：
10升玻璃反应器配机械搅拌，温度计，在氮气保护下加入原料2-氯-5-苯基吡啶500g，一定量的碘化亚铜和N,N'-二甲基-1,2-环己二胺，相对于原料2-氯-5-苯基吡啶1.1摩尔当量的碘化钾，3升N-甲基吡咯烷酮作为溶剂，加热至180℃反应，当体系内无原料2-氯-5-苯基吡啶剩余时停止反应，降至室温，减压蒸馏回收溶剂N-甲基吡咯烷酮，以便下次套用，向反应器内剩余物中加入2升1,2-二氯乙烷，搅拌半小时，抽滤，滤液浓缩干，得到产物2-碘-5-苯基吡啶粗品，向产物粗品中加入一定量的乙醇，进行重结晶，得到产物纯品，摩尔收率为82%。
由此可见，本发明中公开的制备2-碘-5-苯基吡啶的方法可以得到高产率的目标产物，合成方法简单，工艺条件安全稳定，适用于规模化生产，为制备2-碘-5-苯基吡啶提供了一种新的思路和方法。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的仅为本发明的优选例，并不用来限制本发明，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (3)
1.一种制备2-碘-5-苯基吡啶的方法，其特征在于，选用2-氯-5-苯基吡啶为初始原料，在催化剂和配体存在的条件下，与无机碘盐进行卤素置换反应，经过简单后处理即可得到2-碘-5-苯基吡啶；
反应过程的具体制备步骤如下：
(1)卤素置换：氮气保护下，将2-氯-5-苯基吡啶与催化剂和配体，无机碘盐，反应溶剂混合，加热反应至无原料2-氯-5-苯基吡啶剩余，降温进行后处理；
(2)后处理：减压蒸馏回收反应溶剂，加提取溶剂提取反应产物，抽滤分离不溶物，浓缩提取溶剂得到产物2-碘-5-苯基吡啶粗品，用重结晶方法纯化得到纯品产物；
步骤(1)所用催化剂为卤化亚铜盐，配体为1,10-菲罗啉、1,2-环己二胺和N,N'-二甲基-1,2-环己二胺，无机碘盐为碘化钠或碘化钾，反应溶剂为二甲基亚砜、N,N-二甲基甲酰胺和N-甲基吡咯烷酮，反应温度为100至200℃；步骤(2)中提取溶剂为四氢呋喃、甲苯、乙酸乙酯和1,2-二氯乙烷，重结晶溶剂为甲醇、乙醇和异丙醇。
2.根据权利要求1所述的制备2-碘-5-苯基吡啶的方法，其特征在于：步骤(1)所用催化剂为溴化亚铜或碘化亚铜，配体为1,2-环己二胺和N,N'-二甲基-1,2-环己二胺，无机碘盐为碘化钠或碘化钾，反应溶剂为N,N-二甲基甲酰胺和N-甲基吡咯烷酮，反应温度为100至200℃；步骤(2)中提取溶剂为乙酸乙酯和1,2-二氯乙烷，重结晶溶剂为甲醇和乙醇。
3.根据权利要求1所述的制备2-碘-5-苯基吡啶的方法，其特征在于，步骤(1)所用催化剂为碘化亚铜，配体为N,N'-二甲基-1,2-环己二胺，无机碘盐为碘化钾，反应溶剂为N-甲基吡咯烷酮，反应温度为180℃；步骤(2)中提取溶剂为1,2-二氯乙烷，重结晶溶剂为乙醇。
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