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. Collision-induced dissociation (CID) of S-alkylsulfonium cations proceeds only by the elimination of entire S-alkyl group yielding protonated molecule of the analyte. This process can be useful for a reliable determination of target aromatic heterocyclic compounds in complex mixtures. The applicability of the method is illustrated by the analysis of deasphalted medium petroleum sample. The proposed derivatization principle is considered to be highly applicable as an alternative approach to routine characterization and sensitive determination of most typical sulfur-containing compounds and particularly of aromatic S-heterocycles in crude oils by soft-ionization mass spectrometry methods. © 2023