The synthesis, solvolysis and rearrangement of benzyl trifluoromethanesulfinates

Samuel Braverman, Haim Manor

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12 Scopus citations

Abstract

The synthesis and reactivity of benzyl trifluoromethanesulfinates have been investigated. These esters are easily and almost quantitatively obtained by selective oxidation of the corresponding sulfenates. A study of their behavior has revealed some unique features. In sharp contrast to benzyl arenesulfinates, which undergo ethanolysis with complete sulfur-oxygen bond fission, the corresponding trifiuoromethanesulfinates undergo ethanolysis with exclusive carbon-oxygen bond fission, and with a rate enhancement by a factor of 6 powers of ten. The unusual high reactivity of these esters, comparable to that of the corresponding tosylates, is discussed. A kinetic study of the solvent and substituent effects on the rate of solvolysis has been performed. Also in contrast with benzyl arenesulfinates, these esters undergo facile rearrangement to sulfone on heating in polar nonhydroxylic solvents such as acetonitrile, in high yields. The mechanisms of solvolysis and rearrangement are discussed.

Original languageEnglish
Pages (from-to)357-365
Number of pages9
JournalPhosphorus, Sulfur and Silicon and the Related Elements
Volume53
Issue number1-4
DOIs
StatePublished - 1 Jul 1990

Bibliographical note

Funding Information:
One of us (H. M.) thanks the National Council for Research and Development for the award of a scholarship.

Keywords

  • Benzyl trifluoromethanesulfinates
  • highly reactive sulfinates
  • rearrangement
  • solvent and substituent effects
  • solvolysis
  • synthesis

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