Reactions of tert-butylsulfinyl chloride with tert-butyl hydroperoxide and tert-butyl hydrodisulfide in the presence of pyridine. Observation of 1H CIDNP effects

✍ Scribed by Ido P. Bleeker; Jan B. F. N. Engberts

• Publisher: Elsevier Science
• Year: 2010
• Tongue: English
• Weight: 345 KB
• Volume: 100
• Category: Article
• ISSN: 0165-0513
• DOI: 10.1002/recl.19811001206

✦ Synopsis

Abstract

tert‐Butylsulfinyl chloride (1) reacts smoothly with tert‐butyl hydroperoxide (2) in the presence of pyridine to afford a variety of products including pyridinium tert‐butylsulfonate, tert‐butyl tert‐butylthiolsulfonate, tert‐butanol and tert‐butylsulfonyl chloride. The mechanistic pathway most likely involves homolytic cleavage of the initially formed tert‐butyl tert‐butyl‐peroxysulfinate (5) via a radical cage process. ^1^H CIDNP effects provide strong evidence in support of the radical pair mechanism. The homolytic dissociation of 5 contrasts with the preferred heterolytic cleavage of peroxysulfonates.

Under similar reaction conditions, 1 reacts with tert‐butyl hydrodisulfide (3) to afford tert‐butylsulfinyl tert‐butyldisulfide (13) in a yield of 90%. As compared with 5, thermal decomposition of 13 is much slower, reflecting the higher SOS bond dissociation energy in 13, relative to the low OO bond dissociation energy in 5. At elevated temperatures, 13 yields tert‐butyl tert‐butylthiolsulfonate and di‐tert‐butyl tetrasulfide, probably via a homolytic pathway.