Abstract
A new type of fragmentation of organic cation radicals of sulfides, sulfoxides, and sulfones, leading to the elimination of S+, SO+ and SO2+ ions, respectively, has been discovered, and the possible mechanisms of their formation have been proposed. The most probable is a mechanism by which a cleavage of two C-S bonds takes place in the cyclic transition complex and formation of one C-C bond due to the recombination of the radicals. The line of the ion with a mass of 32 amu present in the spectra of almost all the sulfoxides studied, was assigned to the sulfur ion, formed by a similar mechanism after the displacement of alkyl or aryl residue in the molecular ion from sulfur to oxygen. Signs of such a migration also appear in the mass spectra of certain sulfones.
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