Reaction of Sulfoxides with Acylating Reagents. IV. The Catalytic Effect of Both the Brönsted and Lewis Acids in the Oxygen Exchange Reaction of Diaryl Sulfoxides with Acetic Anhydride

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概要

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• Diaryl sulfoxides undergo oxygen exchange and racemization reaction with acetic anhydide. The rate of racemization of <I>p</I>-tolyl phenyl sulfoxide was found to be twice that of oxygen exchange. The remarkably small substituents effect is also in keeping with the S<SUB>N</SUB>2 type mechanism. Addition of acetic acid increases the rate of both the racemization and oxygen exchange. Racemization of sulfoxides is also known to be catalyzed markedly by a small amount of Lewis acid. When the reaction was carried out in the presence of a small amount of both acetic acid and Lewis acid, the ratio of the rate constants, <I>k</I><SUB>ex</SUB>⁄<I>k</I><SUB>rac</SUB> becomes unity. This may mean that the presence of both Brönsted and Lewis acids facilitates the cleavage of S–O bond by easy protonation (or hydrogen-bonding) or coordination on the sulfoxide oxygen, and the assistance of the nucleophilic attack by acetate becomes less important in the reaction. The larger substituent effect is also in keeping with the S<SUB>N</SUB>1 type mechanism.

• 公益社団法人 日本化学会の論文

著者

• Oae Shigeru

  Deparment of Applied Chemistry Faculty of Engineering Osaka City University

• Kise Masahiro

  Department of Applied Chemistry, Faculty of Engineering, Osaka City University

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