Gas phase thermolyses. Part 4. Gas phase thermolyses of thietan 1-oxide and 1,2-oxathiolan 2-oxide. Evidence for the intermediacy of 1,2-oxathiolan

Abstract

The unimolecular gas phase thermolyses of thietan 1-oxide, 1,2-oxathiolan 2-oxide, and dimethyl sulphoxide have been studied by the flash vacuum thermolysis–field ionization mass spectrometry technique in the temperature range 783–1 404 K. The reactions are rationalized in terms of atomic oxygen extrusions and sulphoxide–sulphenate rearrangements. Evidence is presented for the common intermediacy of 1,2-oxathiolan from the thermolyses of both thietan 1-oxide and 1,2-oxathiolan 2-oxide.