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

Chattopadhyaya, Jyoti B. ; Rama Rao, A. V. (1974) Electron-impact fragmentation of triaryl-s-trithianes: a novel skeletal rearrangement involving sulphur-sulphur bond formation Organic Mass Spectrometry, 9 (7). pp. 649-659. ISSN 0030-493X

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/oms.121...

Related URL: http://dx.doi.org/10.1002/oms.1210090704

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.

Item Type:Article
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