Influence of Br- concentration on (Br)+-mediated indirect electrooxidation of alcohols to the corresponding carbonyl compounds.

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概要

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• Current efficiency for the (Br)<SUP>+</SUP>(positive bromine species)-mediated indirect electrooxidation of alcohols to the corresponding carbonyl compounds decreased with increase in Br<SUP>−</SUP> concentration in dichloromethane and aqueous acidic solutions, while no concentration dependence was observed in an aqueous neutral solution. These facts suggested a general and practical guideline for the indirect electrooxidation, i.e. low Br<SUP>−</SUP> concentration is favorable in an electrolytic solution of low nucleophilicity. It was also found that the kind of (Br)<SUP>+</SUP> species formed anodically in the absence of the alcohols in dichloromethane clearly depended on charge(<I>Q</I>) passed as follows: Br<SUB>3</SUB><SUP>−</SUP> at <I>Q≤</I>2⁄3F mol<SUP>−1</SUP> (1F=96480 C), Br<I><SUB>n</SUB></I><SUP>−</SUP> (<I>n</I>>3) at 2⁄3<<I>Q</I><1F mol<SUP>−1</SUP>, and Br<SUB>2</SUB> at <I>Q</I>=1F mol<SUP>−1</SUP>. Among these species, Br<SUB>3</SUB><SUP>−</SUP> and Br<SUB>2</SUB> seemed to be the weakest and strongest oxidizing agents, respectively. Lower efficiency for the indirect electrooxidation in higher Br<SUP>−</SUP> concentration was rationalized as due to more predominant formation of Br<SUB>3</SUB><SUP>−</SUP> and/or Br<I><SUB>n</SUB></I><SUP>−</SUP> with smaller <I>n</I> values.

• 公益社団法人 日本化学会の論文

著者

• Nonaka Tsutomu

  Department Of Electric Chemistry Tokyo Institute Of Technology

• Takiguchi Tsuyoshi

  Department of Electronic Chemistry, Tokyo Institute of Technology

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