CN109422692A - 一种2,4,5-三取代咪唑化合物的制备方法 - Google Patents

一种2,4,5-三取代咪唑化合物的制备方法 Download PDF

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CN109422692A
CN109422692A CN201710729175.XA CN201710729175A CN109422692A CN 109422692 A CN109422692 A CN 109422692A CN 201710729175 A CN201710729175 A CN 201710729175A CN 109422692 A CN109422692 A CN 109422692A
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substituted imidazole
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CN109422692B (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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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

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Abstract

本发明涉及到一种制备2,4,5‑三取代咪唑的方法。该方法以卞胺为底物，在可见光光照条件下，ZnIn2S4作为光催化剂，卞胺发生光催化的环化，得到2,4,5‑三取代咪唑化合物。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2,4,5-三取代咪唑化合物的制备方法
技术领域
本发明涉及到2,4,5-三取代咪唑化合物的制备方法。
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2,4,5-三取代咪唑化合物。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
本发明提供一种三取代的咪唑化合物的制备方法。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：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2,4,5-三取代咪唑化合物。
所用ZnIn2S4催化剂与底物的质量比为：0.1-20wt％。
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ZnIn2S4和醇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2,4,5-三取代咪唑化合物核磁图。
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1。
表1卞胺光催化环化制备的2,4,5-三取代咪唑化合物
分析表2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9-17，将0.1g胺底物，0.01g 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2。
表2不同胺类底物光催化环化制备2,4,5-三取代咪唑化合物
分析表2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2,4,5-三取代咪唑化合物。

Claims (6)

1.一种2,4,5-三取代咪唑化合物的制备方法，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ZnIn2S4作用，卞胺发生光催化的环化，得到2,4,5-三取代的咪唑化合物。
2.根据权利要求1所述的方法，其特征在于：
所述2,4,5-三取代的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中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，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。
6.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。
CN201710729175.XA 2017-08-23 2017-08-23 一种2,4,5-三取代咪唑化合物的制备方法 Active CN109422692B (zh)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103908971A (zh) * 2014-04-16 2014-07-09 福州大学 一种用于选择性催化氧化偶联胺生成亚胺的光催化剂

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103908971A (zh) * 2014-04-16 2014-07-09 福州大学 一种用于选择性催化氧化偶联胺生成亚胺的光催化剂

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* Cited by examiner, † Cited by third party
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XIANJUN LANG等: "Selective Formation of Imines by Aerobic Photocatalytic Oxidation of Amines on TiO2", 《ANGEW. CHEM. INT. ED.》 *

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