Gas-phase thermolyses. Part 7. Gas-phase thermolysis of 1,2,3-oxadithiolan 2-oxide and thiiran 1-oxide. On the intermediacy of 1,2-oxathietan

Abstract

The unimolecular gas-phase thermolyses of 1,2,3-oxadithiolan 2-oxide and thiiran 1-oxide have been studied by the flash vacuum thermolysis–field ionization mass spectrometry (f.v.t.–f.i.m.s.) technique in the temperature range from 1 043 to 1 404 K. The reactions are rationalized in terms of sulphoxide–sulphenate rearrangement and atomic oxygen, sulphur monoxide, and sulphur dioxide extrusions. Evidence is presented for the common intermediacy of 1,2-oxathietan from the thermolyses of both 1,2,3-oxadithiolan 2-oxide and thiiran 1-oxide.