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.

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