CN109422732A - 一种1,2,4,5-四取代咪唑的制备方法 - Google Patents

一种1,2,4,5-四取代咪唑的制备方法 Download PDF

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CN109422732A
CN109422732A CN201710729016.XA CN201710729016A CN109422732A CN 109422732 A CN109422732 A CN 109422732A CN 201710729016 A CN201710729016 A CN 201710729016A CN 109422732 A CN109422732 A CN 109422732A
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CN109422732B (zh
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王峰
王敏
李利花
罗能超
张晓辰
刘美江
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明涉及到一种1,2,4,5‑四取代咪唑的制备方法。该方法以卞胺为底物，在可见光光照条件下，Mo掺杂ZnIn2S4(Mo‑ZnIn2S4)作为光催化剂，卞胺发生光催化的环化，得到1,2,4,5‑四取代咪唑化合物。本发明提供了一种新的取代咪唑化合物的制备方法，条件温和，产品收率高，具有很好的应用前景。

Description

一种1,2,4,5-四取代咪唑的制备方法
技术领域
本发明涉及到一种1,2,4,5-四取代咪唑的制备方法。
背景技术
咪唑是一类重要的化工原料，是精细化学品和大宗工业化学品合成的重要中间体，广泛应用于制药、香料、农业化学品、聚合物等。传统的取代咪唑的合成方法，采用醛、酮和含氮化合物，或者采用亚胺和酰氯等多种原料为底物，通过缩合反应生成。所采用原料复杂，反应条件苛刻。本发明采用卞胺作为单一原料，在光照条件下，室温下就可以发生环化，生成1,2,4,5-四取代咪唑化合物。本方法所得取代咪唑的收率高，产物和催化剂易分离，条件温和，后处理简单；催化剂易于重复使用，具有很好的应用前景。
发明内容
本发明提供一种1,2,4,5-四取代咪唑的制备方法。该方法以卞胺及其衍生物为底物，在可见光光照条件下，在催化剂为ZnIn2S4催化剂作用，卞胺发生光催化的环化，得到取代的咪唑化合物。
所述三取代的咪唑化合物结构如下：其中R为苯基及苯环取代的衍生物，或者呋喃和噻吩.所述苯环取代的衍生物，取代基为氟、氯、溴、甲基、甲氧基等中的一种或者二种以上，取代基个数为1-5个。
所述卞胺及其衍生物中衍生物指的是苯环取代的衍生物，取代基为氟、氯、溴、甲基、甲氧基等中的一种或者一种以上，取代基个数为1-5个；2-胺甲基呋喃和2-胺甲基噻吩。
在可见光激发下，底物分子本身不会吸光，需要采用光催化剂，本发明发现ZnIn2S4可以实现在可见光作用下，三分子卞胺发生环化，生成1,2,4,5-四取代咪唑化合物。
所用Mo-ZnIn2S4催化剂与底物的质量比为：0.1-20wt％。Mo的掺杂量影响到催化剂的催化性能，本发明采用的钼掺杂的硫化铟锌Mo-ZnIn2S4,Mo与Zn的摩尔比1-20：100。
可见光的波长为400-500nm。
为了使底物与催化剂充分接触，特别是一些胺类化合物室温下是固体，需要加入溶剂使其溶解，所用溶剂为乙腈、甲苯、四氢呋喃、乙醇中一种或者一种以上。
本发明反应操作过程如下：将催化剂Mo-ZnIn2S4和卞胺加入到石英玻璃光中，再加入适量溶剂，密闭反应釜，通过氩气置换关内气体，用玻璃塞盖住口。在9.6W 455nm，LED光反应器下反应一定时间后，冷却，离心分离催化剂，催化剂用乙醇和丙酮洗涤，80℃干燥后重复使用。
产品的定性采用气相色谱-质谱分析，并和标准样品的保留时间进行比对；定量用内标法气相色谱分析。
本发明提供了一种新的1,2,4,5-四取代咪唑化合物的制备方法，条件温和，产品收率高，具有很好的应用前景。
本发明具有如下特点：催化剂体系简单、高效，副产物少，催化剂用量少，催化剂与产物易分离，催化剂可循环使用。
附图说明
图1实施例1中合成1,2,4,5-四取代咪唑核磁图。
具体实施方式
下面通过具体实施例对本发明进行说明，但本发明实施不局限于这些实施例：
实施例1-8：将0.1g卞胺，一定量的Mo与Zn的摩尔比为4％的Mo-ZnIn2S4，2mL溶剂加入到5mL石英反应管中，通入氩气置换，密闭反应管，磁子搅拌，在9.6W455nm，LED光反应器下反应一定时间后，离心分离催化剂。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表1。
表1卞胺光催化环化制备的1,2,4,5-四取代咪唑化合物
分析表1中结果可知，咪唑收率随着催化剂用量增加和反应时间延长而增加。在不同反应溶剂中乙腈、甲苯、四氢呋喃和乙醇等溶剂中，都有比较好的效果。
实施例9-13：将0.1g卞胺，0.01g不同Mo掺杂量的Mo-ZnIn2S4，2mL溶剂加入到5mL石英反应管中，通入氩气置换，密闭反应管，磁子搅拌，在9.6W 455nm，LED光反应器下反应一定时间后，离心分离催化剂。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表2。
表2卞胺光催化环化制备的1,2,4,5-四取代咪唑化合物
分析表2中结果可知，随着Mo掺杂量的增加，1,2,4,5-四取代咪唑化合物收率逐渐增加，当掺杂量超过5％之后，1,2,4,5-四取代咪唑化合物收率逐渐增加有所下降。因此，Mo掺杂量需要达到一个适中的量，才会得到好的催化效果
实施例14-22，将0.1g胺底物，0.01g Mo与Zn的摩尔比为5％的Mo-ZnIn2S4，2mL乙腈加入到5mL石英反应管中，通入氩气置换，密闭反应管，磁子搅拌，在9.6W 455nm，LED光反应器下反应24小时后，离心分离催化剂。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表3。
表3不同胺类底物光催化环化制备1,2,4,5-四取代咪唑化合物
分析表3中结果可知，不同基团取代的卞胺，2-胺甲基呋喃和2-胺甲基噻吩都可以得到1,2,4,5-四取代咪唑化合物。实例20所示，位组大的卞胺，四取代咪唑化合物收率不高。

Claims (7)

1.一种1,2,4,5-四取代咪唑的制备方法，其特征在于：该方法以卞胺及其衍生物中的一种为底物，在可见光光照条件下，在催化剂作用下，卞胺发生光催化的环化，得到1,2,4,5-四取代的咪唑化合物，所述催化剂为钼掺杂的硫化铟锌Mo-ZnIn2S4。
2.根据权利要求1所述的方法，其特征在于：
所述1,2,4,5-四取代咪唑化合物结构如下：R为苯基或苯环取代的衍生物，或者呋喃或噻吩，所述苯环取代的衍生物，取代基为氟、氯、溴、甲基、甲氧基等中的一种或者二种以上，取代基个数为1-5个。
3.根据权利要求1所述的方法，其特征在于：所述卞胺及其衍生物中衍生物指的是卞胺苯环取代的衍生物或者为2-胺甲基呋喃和2-胺甲基噻吩中的一种或者二种以上，取代基为氟、氯、溴、甲基、甲氧基等中的一种或者二种以上，取代基个数为1-5个。
4.根据权利要求1所述的方法，其特征在于：所用催化剂与底物的质量比为：0.1-20wt％，优选5-20h；反应时间为2-48h，优选12-24h。
5.根据权利要求1所述的钼掺杂的硫化铟锌Mo-ZnIn2S4,Mo与Zn的摩尔比1-20：100，优选3-10:100。
6.根据权利要求1所述的方法，其特征在于：采用溶剂为乙腈、甲苯、四氢呋喃、乙醇中一种或者二种以上。
7.根据权利要求1所述的方法，其特征在于：可见光的波长为400-500nm。
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Cited By (1)

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CN112264049A (zh) * 2020-10-14 2021-01-26 盐城工学院 一种用于光催化固氮合成氨的Mo或Fe掺杂Zn1-xIn2S4催化剂的制备方法

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* Cited by examiner, † Cited by third party
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CN112264049A (zh) * 2020-10-14 2021-01-26 盐城工学院 一种用于光催化固氮合成氨的Mo或Fe掺杂Zn1-xIn2S4催化剂的制备方法
CN112264049B (zh) * 2020-10-14 2023-08-25 盐城工学院 一种用于光催化固氮合成氨的Mo或Fe掺杂Zn1-xIn2S4催化剂的制备方法

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