On the Mechanism of Sulfonamide Cleavage by Arene Anion Radicals

W. D. Closson, Sungchul Ji, Shirley Schulenberg

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Abstract

In the cleavage of sulfonamides of secondary amines with arene anion radicals 2 moles of the reducing species are consumed rapidly, resulting in formation of amide and sulfinate anions. In the case of arenesulfinate ion a subsequent, much slower reduction converts this to arene hydrocarbon and a mixture of thiosulfate, sulfite, and sulfide salts. By analysis of competitive reactions, the rate law for the first step has been deduced as rate = k[anion radical][sulfonamide]. In the reaction of sodium naphthalenide (and probably sodium biphenylide) with the toluenesulfonamide of p-toluidine, electron transfer and cleavage are considerably faster than acid-base reaction with the acidic proton. Sodium anthracenide, however, reacts only as a base with this substrate. Gross structural effects on the scope of the reaction are discussed.

Original languageEnglish (US)
Pages (from-to)650-657
Number of pages8
JournalJournal of the American Chemical Society
Volume92
Issue number3
DOIs
StatePublished - Feb 1 1970
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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