Convenient high resolution mass spectrometry characterization of aromatic sulfur-containing petroleum components following by preliminary S-alkylation with aliphatic alcohols.

This paper describes rather suitable and variable preliminary derivatization strategy that may precede the molecular level characterization of sulfur-containing compounds of a particularly aromatic nature by high-resolution MALDI and ESI mass spectrometry. We demonstrated for the first time that free aliphatic alcohols (primary 1-alkanols C3-C20) in the presence of triflic acid provide easy S-alkylation of not only saturated sulfides but also most typical aromatic sulfur-containing compounds (benzothiophene, dibenzothiophene and their homologues) widely distributed and frequently analyzed in oil. The reaction proceeds quantitatively at rather mild conditions and gives rise to corresponding S-alkyl sulfonium salts the cation moieties of which can be detected using MALDI and ESI mass spectrometry with excellent signal/noise (S/N) ratios; the response ratios for target ions being quite close for both methods.