电化学方法固定CO_2用于2-羟基-2-(4-甲氧基苯基)-丙酸甲酯的合成  

Electrosynthesis of 2-Hydroxy-2-( 4-methoxy-phenyl) -propionic Acid Methyl Ester via Electrochemical Fixation of Carbon Dioxide

作　　者：张凯[1] 吴腊霞[1] 胡磊磊[1] 丁小燕[1] 王欢[1] 陆嘉星[1] 

机构地区：[1]上海市绿色化学与化学工程绿色化重点实验室,华东师范大学化学系,上海200062

出　　处：《高等学校化学学报》2010年第7期1410-1415,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20973065);上海市重大基础研究项目(批准号:08dj1400100);上海市重点学科项目(批准号:B409)资助

摘　　要：在一室型电解池中,以饱和CO2的N,N-二甲基甲酰胺(DMF)为溶液,Mg为牺牲阳极,不锈钢、钛、铜、镍和银为工作电极,通过电化学方法固定CO2,在恒电流电解的条件下研究了对甲氧基苯乙酮的电羧化反应,得到了重要的有机合成中间体2-羟基-2-(4-甲氧基苯基)-丙酸甲酯.电羧化产率受支持电解质种类、电极材料、电流密度、电解电量和反应温度等影响.经过反应条件的优化,目标产物在恒定电流密度为5.0mA/cm2的条件下产率达到63%.同时,以玻碳电极-Pt丝螺旋电极-Ag/AgI/I-为三电极体系,研究了对甲氧基苯乙酮的电化学行为,根据底物在通入CO2前后循环伏安图的变化推测了对甲氧基苯乙酮的电羧化反应机理.In the one compartment electrochemical cell equipped with magnesium as the sacrificial anode, stainless steel,titanium（ Ti） ,copper（ Cu） ,nickel（ Ni） ,silver（ Ag） as the cathode and in the DMF solution saturated with carbon dioxide,the aimed product 2-hydroxy-2-（ 4-methoxy-phenyl） -propionic acid methyl ester was electrosynthesized via electrochemical fixation of carbon dioxide. Under the various controlled current conditions,the electrocarboxylation of p-methoxylacetophenone was also measured as a function of supporting electrolytes,cathode materials,the current density,passed charge and temperatures. During the systematic investigation,the maximal yield of 63% was achieved when the electrolysis was carried out under a controlled current density of 5. 0 mA/cm2 until theoretical charge passed through the cell. Furthermore,the electrochemical behavior of p-methoxylacetophenone has been studied in a three-electrode system,a glassy carbon as the working electrode（ d = 2 mm） ,a platinum（ Pt） spiral as the counter electrode and Ag/AgI/0. 1 mol/L TBAI in DMF as the reference electrode. From analysis of cyclic voltammograms of p-methoxylacetophenone before and after addition of carbon dioxide,a possible electrocarboxylation mechanism was put forward accordingly.

关 键 词：对甲氧基苯乙酮 二氧化碳 电羧化 恒电流电解 

分 类 号：O646[理学—物理化学]