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以镍为阴极由二氧化碳与芳香酮电合成α-羟基羧酸
引用本文:袁高清,李志发,江焕峰. 以镍为阴极由二氧化碳与芳香酮电合成α-羟基羧酸[J]. 中国化学, 2009, 27(8): 1464-1470. DOI: 10.1002/cjoc.200990246
作者姓名:袁高清  李志发  江焕峰
作者单位:华南理工大学化学与化工学院,广州510640
摘    要:室温下,在一室电解池中,以n-Bu4NBr-DMF作电解质、镍为阴极、铝为阳极,恒电流电解二氧化碳与芳香酮(苯乙酮、对二苯甲酮、6-甲氧基-2-萘乙酮、4-甲基苯乙酮和4-甲氧基苯乙酮),可以得到相应的α-羟基羧酸(产率56%-90%)。实验结果显示,阴极材料、芳香族酮的结构以及电解条件(如电量、底物浓度、导电盐、溶剂和二氧化碳压力等)对目标产物的产率有很大影响;反应系统中质子剂(水)的存在将导致副产物频哪醇的生成。本文还根据循环伏安实验和合成实验结果简要地讨论了反应机理。

关 键 词:二氧化碳  电合成  α-羟基羧酸  苯乙酮  电羧化反应
收稿时间:2008-11-25
修稿时间:2009-01-16

Electrosyntheses of α ‐Hydroxycarboxylic Acids from Carbon Dioxide and Aromatic Ketones Using Nickel as the Cathode
Gaoqing YUAN,Zhifa LI,Huanfeng JIANG. Electrosyntheses of α ‐Hydroxycarboxylic Acids from Carbon Dioxide and Aromatic Ketones Using Nickel as the Cathode[J]. Chinese Journal of Chemistry, 2009, 27(8): 1464-1470. DOI: 10.1002/cjoc.200990246
Authors:Gaoqing YUAN  Zhifa LI  Huanfeng JIANG
Affiliation:1. Tel.: 0086‐020‐22236518;2. Fax: 0086‐020‐87112906;3. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong 510640, China
Abstract:With Ni as the cathode and Al as the anode, aromatic ketones (acetophenone, benzophenone, 6‐methoxy‐2‐acetonaphthone, 4‐methylacetophenone and 4‐methoxyacetophenone) could be successfully electrocarboxylated with CO2 (4 MPa) in an undivided cell containing n‐Bu4NBr‐DMF electrolyte at a constant current under room temperature, affording the corresponding α‐hydroxycarboxylic acids in good to excellent yields (56%–90%). The experimental results showed that the yields of the target products were strongly dependent on the nature of cathode materials and aromatic ketones as well as electrolytic conditions (such as electricity, substrate concentrations, conducting salts and solvents, CO2 pressure). In addition, it was found that the presence of protic agent such as water would lead to the increase of pinacol byproducts. The reaction mechanism was briefly discussed by CV experiments.
Keywords:carbon dioxide  electrosynthesis  α‐hydroxycarboxylic acid  acetophenone  electrocarboxylation
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