Abstract

AbstractA series of pyrilium hydrochlorides (Py+ClO−4) have been studied by means of both electron ionization and fast‐atom bombardment (FAB) methods. Only for some compounds does electron ionization show the formation of Py+, together with [Py—H]+· ions. Metastable ion data indicate that the former also originate through H· loss when their formation could be explained by loss of perchloric acid through a thermal process directly from the salt. Many fragment ions, related to the original structures, are also detected. In contrast, in FAB conditions, all the compounds show the formation of Py+ without any fragmentation products, proving its effectiveness in the easy identification of the related molecular species. Only by the mass‐analyzed ion kinetic energy spectra of Py+ ions can a valid characterization of the compounds under study be achieved.

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