10490-22-9Relevant articles and documents
Reactions of tert-butylsulfinyl chloride with tert-butyl hydroperoxide and tert-butyl hydrodisulfide in the presence of pyridine. Observation of 1H CIDNP effects
Bleeker, Ido P.,Engberts, Jan B. F. N.
, p. 459 - 461 (2007/10/02)
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-butylperoxysulfinate (5) via a radical cage process. 1H 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 90percent.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.
