Buffer Catalysis of the Hydrolysis of Phenyl and Methyl Benzenesulfinates. Contrasting Behavior between Acyclic and Cyclic Analogs.

• Okuyama Tadashi

  Faculty of Engineering Science, Osaka University

Bibliographic Information

Other Title

• Buffer Catalysis of the Hydrolysis of P

Abstract

The hydrolysis of phenyl benzenesulfinate is catalyzed by both acid and base, and is strongly accelerated by the carboxylate and amine base components of the buffer. Carboxylates and amines constitute different groups in the Brønsted plots, falling nearly on two separate lines of β = 1. The carboxylates are about 400-times more effective catalysts than the amines of similar basicity. Solvent deuterium isotope effects on the catalytic constants are small, and the buffer catalysis is considered to be nucleophilic. By contrast, the hydrolysis of the methyl ester was only weakly affected by the buffer, if at all. High efficiencies of oxygen nucleophiles in the catalysis of the hydrolysis of acyclic sulfinates are distinctive compared with the cyclic analogs, and are rationalized by a concerted S_N2-like mechanism of the nucleophilic reaction at sulfur.

Journal

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 69 (11), 3281-3287, 1996

  The Chemical Society of Japan

Keywords

• General Chemistry

Details

• CRID: 1390001204122340992
• NII Article ID: 130004149364
• NII Article ID: 10008911212
• NII Book ID: AA00580132
• DOI: 10.1246/bcsj.69.3281
• ISSN: 13480634
• ISSN: 00092673
• NDL BIB ID: 4098867
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I4098867
• Web Site: https://academic.oup.com/bcsj/article-pdf/69/11/3281/56194713/bcsj.69.3281.pdf
• Text Lang: en
• Data Source:
  • JaLC
  • NDL
  • Crossref
  • CiNii Articles
• Abstract License Flag: Disallowed