Electron-impact fragmentation of triaryl-s-trithianes: a novel skeletal rearrangement involving sulphur-sulphur bond formation

Abstract

The mass spectral fragmentation of seven substituted 2,4,6-triaryl-s-trithianes has been studied and the fragmentation modes confirmed by deuterium labelling. Triphenyl-s-trithiane shows some interesting features in its mode of cleavage and does not eliminate S, S₂, SH^⋅, H²S or S₂H^⋅ from its molecular ion. The prominent radical ions in the mass spectrum are at m/e 180 (52.3%) and m/e 186 (45.2%), corresponding to stilbene and PhCHS₃. Their compositions have been established by deuterium labelling and accurate mass measurements. The formation of stilbene indicates a relationship between pyrolytic and electron-impact studies. The origin of [PhCHS₃]^+⋅ suggests that one of the sulphur atoms attaches itself to the other two sulphur atoms in the molecular ion, eliminating a stilbene radical ion. The other important fragmentation corresponds to the monomer radical ion (thiobenzaldehyde) and the thiobenzoyl cation. Among the other substituted triaryl-s-trithianes with substituents such as chloro, methoxy, methylenedioxy and hydroxy groups on the phenyl ring (IV to IX), only the tris-(p-chlorophenyl)-s trithiane shows an insignificant molecular ion. Unlike the triphenyl derivative, the chloro, methoxy and methylenedioxy derivatives show the loss of HS^⋅ and/or H₂S from the molecular ion. The spectrum of tris-(p-hydroxyphenyl)-s-trithiane corresponds to the spectrum of p-hydroxythiobenzaldehyde.