Mass spectrometric studies. XII. Organic sulphates

Abstract

The mass spectra of dimethyl and diethyl sulphates contain intense rearrangement ions resulting from expulsion of sulphur trioxide subsequent to α-cleavage. The cyclic sulphates from 1,2-diols fragment quite differently to the analogous sulphites, and the mode of fragmentation appears to depend in a non-specific way on the substituents present. The sulphates of 1,3-diols fragment in an orderly manner via M-SO₃ ions, which are best represented as oxetan radical cations, while limited data for sulphates of 1,4-diols suggest fragmentation via tetrahydrofuran-like intermediates.