Pd/C催化Suzuki反应合成4-联苯甲酸  

Pd/C-Catalyzed Synthesis of 4-Bibenzoic Acid via Suzuki-Miyaura Coupling Reaction

作　　者：薛智 戴先芝 余列 杨子松 洪一艳 蒲有棋 周艳 黄飞 Zhi Xue;Xianzhi Dai;Lie Yu;Zisong Yang;Yiyan Hong;Youqi Pu;Yan Zhou;Fei Huang(College of Resources&Environment,Aba Teachers University,Wenchuan 623002,Sichuan Province,China;School of Resource and Environmental Engineering,Yibin University,Yibin 644000,Sichuan Province,China)

机构地区：[1]阿坝师范学院资源与环境学院,四川汶川623002 [2]宜宾学院资源与环境工程学院,四川宜宾644000

出　　处：《大学化学》2022年第5期181-185,共5页University Chemistry

基　　金：四川省科技计划项目(2020JDRC0064);阿坝师范学院校级重点项目(ASA20-04)。

摘　　要：通过芳基卤代物和芳基硼酸合成联苯类化合物的Suzuki-Miyaura偶联反应被广泛应用于天然产物,药物和功能材料的合成。然而目前本科教学中极少有相关实验,主要是由于传统的Suzuki反应条件通常需要昂贵的含配体Pd催化剂,反应溶剂大多含有诸如甲苯或者1,4-二氧六环等有毒害溶剂,反应过程需要惰性气体氛围,且大多需在加热反应8 h以上。这些限制极大地阻碍了本科生开展这一重要的有机化学实验。本文介绍了改进的Suzuki反应条件:无配体Pd/C作为催化剂,乙醇和水的混合溶剂作为反应溶剂,并且室温搅拌半小时反应即可结束,反应全程敞口需要空气(氧气)的辅助而不是惰性氛围。在此条件下,以苯硼酸与4-溴苯甲酸为原料,碳酸钾作为碱,高效合成了4-联苯甲酸。相比传统Suzuki反应条件下催化剂均为一次性使用,不可回收,本实验中回收的Pd/C催化剂可循环使用5次以上而几无活性损失。本实验项目从成本,可操作性,绿色环保等角度为本科生熟悉Suzuki反应提供了可能。The Suzuki-Miyaura coupling reaction for the synthesis of biphenyl compounds through aryl halides and aryl boronic acids has been widely used in the synthesis of natural products,drugs,and functional materials.However,there are very few relevant experiments currently in undergraduate teaching,mainly because the traditional Suzuki reaction conditions involve expensive ligand-containing Pd catalysts.Furthermore,most reaction solvents contain toxic solvents such as toluene or 1,4-dioxane,and the reaction requires an inert gas atmosphere and heating for over 8 h.These restrictions largely prevent undergraduates from carrying out this important organic chemistry experiment.In this study,the Suzuki coupling conditions were modified as follows:ligand-free Pd/C was used as the catalyst,ethanol mixed with water was used as the reaction solvent,and then the reaction was stirred at room temperature for 30 min in the open air(oxygen)instead of in an inert atmosphere.Under these conditions,the starting materials,phenylboronic acid and 4-bromobenzoic acid,were reacted using potassium carbonate as the base,which efficiently synthesized 4-bibenzoic acid.Compared to the traditional Suzuki reaction conditions in which the catalyst cannot be recovered,the Pd/C catalyst recovered in this experiment can be recycled more than 5 times without substantial activity loss.This experiment provides the possibility for undergraduates to become familiar with the Suzuki reaction due to improvements in cost,operability,and environmental protection.

关 键 词：4-联苯甲酸 Suzuki-Miyaura反应 PD/C 空气氛围 回收循环使用 

分 类 号：G64[文化科学—高等教育学] O6[文化科学—教育学]