A study of some cations formed in the ammonia chemical ionization of ketones using mass analysed ion kinetic energy spectrometry

The structures of the major adduct ions formed in ammonia chemical ionization of thirteen aliphatic and aromatic ketones have been studied by mass analysed ion kinetic energy spectrometry. The [M+NH 3 +H] + ion is shown to have a protonated carbinolamine structure, [M+2NH 3 +H] + to be a protonated carbinolamine with hydrogen‐bonded ammonia and [2M+NH 3 +H] + to be, at least in part, a protonated carbinolamine with hydrogen‐bonded ketone. These structures may imply a nucleophilic addition of ammonia at the carbonyl of the ketone‐ammonium ion complex. An unusual hydroxy migration is seen in the internal rearrangement of the [2M+NH 3 +H] + ion leading to the formation of a protonated imine.