Chemistry of sulphines. Part XVIII. Electron impact induced rearrangements of arylthio, arylsulphinyl, and arylsulphonyl substituted sulphines

Abstract

The mass spectra of aryl arylthio sulphines (I)–(VII), aryl arylsulphinyl sulphines (VIII)–(XIII) and aryl arylsulphonyl sulphines (XIV)–(XVIII) have been rationalized. All three types of sulphines show a rearrangement involving the intermediacy of an oxathiiran. Arylthio sulphines (I)–(VII) show an oxygen migration of the CSO function to the adjacent sulphur atom. The α-thioxo-sulphoxide thus formed undergoes a 1,2-aryl shift from sulphur to oxygen. Arylsulphinyl sulphines (VIII)–(XIII) show a migration of the R¹CSO group to the adjacent sulphoxide oxygen atom. Migration of the aryl (R²) group to the sulphoxide oxygen atom was not observed. Arylsulphonyl sulphines (XIV)–(XVIII) exhibit almost no loss of the arylsulphonyl group, but migration of the R¹CSO group to the sulphonyl oxygen atom was an important fragmentation route. Specific fragmentation of the diaryl sulphines, e.g. loss of O, S, SO, and SOH from the CSO unit are absent in these sulphines.