The mass spectrometric behaviour of benzohydroxaraic and benzothiohydroxamic acids under electron impact

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Abstract
Primary fragmentation reactions in benzohydroxamic and benzothiohydroxamic acids have been studied and compared with those in benzamides and benzothioamides. Mass‐analysed ion kinetic energy spectra, collisional activation spectra and spectral data from labelled compounds were used to elucidate fragment ion structures and reaction mechanisms. The mass spectra are shown to be dependent on ion source temperature. Losses of O and H2O are proved to be thermal in origin. The formation of an S… HO bond, which is analogous to an intramolecular hydrogen bond in solution chemistry, directs many fragmentation pathways. This seems to be the major factor determining the differences between the mass spectra of benzothiohydroxamic acids and those of the corresponding carbonyl compounds.