Electrochemical oxidation of tetrabutylammonium salts of aliphatic carboxylic acids in acetonitrile
Electrochemical oxidation of tetrabutylammonium salts of aliphatic carboxylic acids in acetonitrile
复制标题
DOI：
10.1149/1.1450616
复制
发表时间：
2002-03-01
影响因子：
3.9
通讯作者：
González, FJ
中科院分区：
文献类型：
--
作者：
Galicia, M;González, FJ
在乙腈介质中，对一系列脂肪族羧酸四丁基铵在玻碳电极上的阳极氧化进行了研究。在不受溶剂阳极氧化干扰的情况下研究了其电化学行为。循环伏安分析表明，电子转移和脱羧反应是逐步进行的。库仑分析表明，整个机制是单电子的。然而，制备规模的电解显示了两个电子转移步骤的干预，导致碳正离子，然后与乙腈和羧酸盐本身反应，形成N-酰胺作为主要产物。提出羧酸根离子和烷基碳正离子选择性地发生两种类型的吸附，即在一小部分活性位点上或在玻璃碳表面存在的官能团上。(C)2002年电化学学会。
The anodic oxidation of a series of tetrabutylammonium aliphatic carboxylates has been performed in acetonitrile on glassy carbon electrodes. The electrochemical behavior was studied without the interference of the anodic oxidation of the solvent. The cyclic voltammetry analysis shows that the electron transfer and the decarboxylation are stepwise. The coulometric analysis shows that the overall mechanism is monoelectronic. However preparative scale electrolysis shows the intervention of two electron-transfer steps leading to carbocations, which then react with the acetonitrile and the carboxylate itself to form N-acylamides as principal products. Two types of adsorption of the carboxylate ions and the alkyl carbocations were proposed to occur selectively, namely, on a small fraction of active sites or on the functional groups existing on the glassy carbon surfaces. (C) 2002 The Electrochemical Society.