Cleavage Reactions of Alkoxy Radicals Produced by Anodic Oxidation of<i>t</i>-Alcohols
作者:Kazuhiro Maruyama、Katsuya Murakami
DOI:10.1246/bcsj.41.1401
日期:1968.6
oxidation of t-alcohols in water - dioxane - sodium hydroxide system has been examined. The possibility of production of t-alkoxy radicals by anodic oxidation of t-alcohols in the electrolytic system was found. The relative ease of bond scission of the intermediate t-alkoxy radical was determined by quantitative analysis of the mixture of ketones produced. The relative rates of cleavage decrease in the order:
研究了叔醇在水-二恶烷-氢氧化钠体系中的阳极氧化。发现了通过电解系统中叔醇的阳极氧化产生叔烷氧基自由基的可能性。通过对所产生的酮混合物进行定量分析来确定中间体叔烷氧基的键断裂的相对容易程度。相对裂解速率依次为:烯丙基>仲丁基>异丙基>乙基>正丙基>正丁基>正戊基>异丁基>甲基。证实了β-氢的超共轭效应和β-位双键对裂解反应速率提高的影响。