Page 179 - 《精细化工》2020年第11期

第 37 卷第 11 期 精 细 化 工 Vol.37, No.11
2020 年 11 月 FINE CHEMICALS Nov. 2020

医药与日化原料
磺酸型离子液体催化芳甲胺与邻苯二胺

“一锅”合成苯并咪唑

1
1
1*
1
耿真真 ，张宏宇 ，尹国辉 ，张月成 1,2* ，赵继全
（1. 河北工业大学 化工学院，天津 300130；2. 河北省绿色化工技术与高效节能重点实验室，天津
300130）
摘要：以磺酸型离子液体 1-甲基-3-(3-磺丙基)咪唑盐酸盐（[MIMPs]Cl）为催化剂，催化芳甲胺与 1,2-苯二胺“一
1
锅”好氧氧化缩合，合成相应的苯并咪唑，通过 HNMR 对产物的结构进行了表征。首先，以苄胺与邻苯二胺
合成 2-苯基苯并咪唑为模型反应，筛选出离子液体催化剂并优化了反应条件，即：以离子液体[MIMPs]Cl
为催化剂〔n([MIMPs]Cl)∶n(邻苯二胺)=1∶4〕，0.1 MPa 氧气作氧化剂，N,N-二甲基甲酰胺为溶剂，n(苄胺)∶
n(邻苯二胺)=2.5∶1.0，反应温度 100 ℃，反应时间 20 h。在该条件下 2-苯基苯并咪唑的分离收率达到 91.3%。
将该条件用于其他芳甲胺与 1,2-苯二胺及含各种取代基的 1,2-苯二胺与苄胺的反应。结果表明，该方法的底
物适用性广泛、对环境友好、以分子氧为唯一氧化剂，无过渡金属催化剂存在，适合于药物中间体的合成。
关键词：磺酸型离子液体；1-甲基-3-(3-磺丙基)咪唑盐酸盐；苯并咪唑；芳甲胺；邻苯二胺；医药原料
中图分类号：TQ626.23 文献标识码：A 文章编号：1003-5214 (2020) 11-2325-07

Sulfonic acidic ionic liquid catalyzing one-pot synthesis of benzimidazoles
from arylmethylamines and o-phenylenediamines

1*
1
1
1
GENG Zhenzhen , ZHANG Hongyu , YIN Guohui , ZHANG Yuecheng 1,2* , ZHAO Jiquan
（1. School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China; 2. Hebei
Provincial Key Lab of Green Chemical Technology & High Efficient Energy Saving, Tianjin 300130, China）
Abstract: A series of benzimidazoles were synthesized from arylmethylamines and 1,2-phenylenediamines
using sulfonic acid ionic liquid 1-methyl-3-(3-sulfopropyl)imidazolium chloride ([MIMPs]Cl) as catalyst in
1
one-pot aerobic oxidative condensation. The products were characterized by HNMR. Firstly, the
condensation of benzylamine with o-phenylenediamine to give 2-phenylbenzimidazole was used as a model
reaction to screen the catalysts and optimize the reaction conditions. The optimal reaction conditions were
obtained as follows: [MIMPs]Cl as catalyst [n([MIMPs]Cl)∶n(o-phenylenediamine)=1∶4], oxygen of 0.1
MPa as oxidant, N,N-dimethylformamide as solvent, n(benzylamine)∶n(o-phenylenediamine) = 2.5∶1.0,
reaction temperature of 100 ℃, and reaction time of 20 h. Under these conditions, the separation yield of
2-phenylbenzimidazole reached 91.3%. The reaction conditions were applied to the reactions of other
arylamines with 1,2-phenylenediamine and 1,2-phenylenediamines containing various substituents with
benzylamine. It was found that the method had a wide range of substrate applicability. This method is
environmentally friendly and suitable for the synthesis of drug intermediates due to its advantage of using
molecular oxygen as oxidant and without transition metal catalysts.
Key words: sulfonic acidic ionic liquids; 1-methyl-3-(3-sulfopropyl)imidazolium chloride; benzimidazoles;
arylmethylamines; o-phenylenediamines; drug materials

收稿日期：2020-05-19; 定用日期：2020-06-30; DOI: 10.13550/j.jxhg.20200416
基金项目：国家自然科学基金（21776056）；河北省自然科学基金（B2018202253）
作者简介：耿真真（1994—），女，硕士生，E-mail：18222969780@163.com。联系人：张月成（1979—），男，教授，E-mail：yczhang@
hebut.edu.cn；赵继全（1963—），男，教授，E-mail：zhaojq@hebut.edu.cn。