A “soft” ionization mass spectrometric study of organic sulfides as sulfonium salts

Abstract

Preliminary conversion of nonpolar organic sulfides into sulfonium salts was proposed for their study and analysis by laser desorption/ionization (MALDI and SALDI) and electrospray/ionization (ESI) mass spectrometry. General possibilities of the methodology proposed were demonstrated on examples of dialkyl sulfides, substituted thiacyclanes, dibenzothiophene, and methionine methyl ester. Various alkyl and aralkyl halides, as well as trimethyl- and triethyloxonium salts were tested as alkylating agents. S-alkylation was shown to proceed quantitatively under mild conditions. MALDI and SALDI mass spectra (a matrix-free nanostructurized target was used in SALDI experiments) displayed only ion peaks corresponding to sulfonium cations whose mass numbers were equal to the sum of molecular weights of sulfides and weight increments of the introduced alkyl and aralkyl groups. Trans-alkylation was observed for benzyl-substituted sulfides. Tandem mass spectrometry provided preliminary data on the fragmentation of ESI-generated sulfonium cations and demonstrated differences in the MS/MS spectra of regioisomers.