Studies in mass spectrometry. Part XIV. Mass spectra of aromatic thioethers. The effect of structural variations on the relative abundance of skeletal rearrangement ions

Abstract

The mass spectra of a number of compounds of the general formula C₆H₅·SR and XC₆H₄·S·CH₃ are discussed. In the first group of compounds (C₆H₅·SR), skeletal rearrangement ions are more abundant when R = CH₃ or when R contains double bonds (R = allyl, C₆H₅) than when R is a larger, saturated alkyl group (R = C₂H₅, n-C₅H₁₁). In the second group (XC₆H₄·S·CH₃), M – SH ions are a common feature of the spectra, but the abundance of such ions is in some cases greatly dependent upon the relative orientation of X and SCH₃ groups. For example, when X = CH₃ or OCH₃, the abundance of the M – SH skeletal rearrangement ions is by far the greatest in the meta-isomers.