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有机化学 ›› 2008, Vol. 28 ›› Issue (9): 1572-1577. 上一篇    下一篇

研究论文

电羧化苯乙烯基苯基酮合成2,4-二苯基-4-丁酮酸

林美玉; 王 欢; 张爱健 ; 张贵荣 ; 陆嘉星*   

  1. 华东师范大学化学系 上海市绿色化学与化工过程绿色化重点实验室 上海 200062
  • 收稿日期:2007-10-13 修回日期:2008-03-20 发布日期:2008-09-20
  • 通讯作者: 陆嘉星

Electrocarboxylation of Benzalacetophenone: Synthesis of 2,4-Diphenyl-4-oxobutanoic acid

LIN, Mei-Yu; WANG, Huan; ZHANG, Ai-Jian ; ZHANG, Gui-Rong ; LU, Jia-Xing*   

  1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry,
    East China Normal University, Shanghai 200062
  • Received:2007-10-13 Revised:2008-03-20 Published:2008-09-20
  • Contact: LU, Jia-Xing

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1578

被引次数

6

研究了常压下以CO2和苯乙烯基苯基酮为原料的电羧化反应. 在一室型电解池中, 用Mg作为辅助电极, 不锈钢、铜、镍、钛、石墨电极等作为工作电极, Ag/AgI为参比电极, 恒电位电解苯乙烯基苯基酮和CO2可得到产物2,4-二苯基-4-丁酮酸. 为提高电解产率, 优化了电解条件, 对影响该反应的溶剂、支持盐、阴极材料、电解电位、底物浓度和温度等因素作了进一步讨论. 实验结果表明, 不同的电解条件下, 苯乙烯基苯基酮的还原性能存在较大差异. 通过变化规律的研究, 找到了各个影响因素的最佳条件为: 反应温度为0 ℃, MeCN作为溶剂, 0.1 mol•L－1 四乙基四氟硼酸铵为支持盐, 不锈钢电极为工作电极, Mg棒为辅助电极, 电解电位是－1.75 V. 在此条件下恒电位电解, 2,4-二苯基-4-丁酮酸的产率可达88%. 在乙腈中还研究了苯乙烯基苯基酮的电化学行为, 推测其电羧化反应经历一个电子传递反应-化学反应-电子传递反应-化学反应(ECEC)过程.

关键词: CO2, 苯乙烯基苯基酮, 电合成, 2,4-二苯基-4-丁酮酸

Electrocarboxylation of benzalacetophenone was studied in the presence of an atmospheric pressure of CO2. The only carboxylic product obtained was 2,4-diphenyl-4-oxobutanoic acid in a one-compartment electrochemical cell equipped with magnesium as the sacrificial anode, copper (Cu), nickel (Ni), titanium (Ti), graphite (C) and stainless steel as the cathode and Ag/AgI as the reference electrode under the controlled potential conditions. Influences of solvents, electrolytes, the cathode materials, electrolysis potentials, the concentrations of substrate and temperatures were studied to improve the electrolysis yield. The results show that the electrolysis conditions have an important influence on the yield. The maximal yield reached 88% when the electrolysis was carried out in MeCN-0.1 mol•L－1 TEABF4 on Mg-stainless steel under a controlled potential of －1.75 V vs. Ag/AgI until 2 F•mol－1 of charge had passed through the cell at 0 ℃. The electrochemical behavior of benzalacetophenone has been studied in MeCN. The mechanism of the electrocarboxylation process involves a one-electron reduction and a chemical reaction followed by another one-electron reduction and a chemical reaction.

Key words: CO2, 2,4-diphenyl-4-oxobutanoic acid, electrosynthesis, benzalacetophenone