Collisionally-induced dissociation mass spectra of organic sulfate anions

• Published in: Perkin 2 : an international journal of physical organic chemistry no. 4; pp. 498 - 506
• Main Authors: Attygalle, AB, Garcia-Rubio, S, Ta, J, Meinwald, J
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 2001
• Subjects: Chemistry; Chemistry, Organic; Chemistry, Physical; Physical Sciences; Science & Technology; REARRANGEMENT; FAST-ATOM-BOMBARDMENT; METABOLITES; LIQUID-CHROMATOGRAPHY; SULFOTRANSFERASES; URINE; GAS-PHASE; SPECTROMETRY; ELECTROSPRAY-IONIZATION; STEROID SULFATES
• ISSN: 1472-779X
• DOI: 10.1039/b009019k

The collisionally-induced dissociation mass spectra of a variety of organic sulfate ester anions are described and mechanistically rationalized. A cyclic syn-elimination pathway, analogous to that of the Cope elimination, is postulated for the commonly observed formation of bisulfate anion (HSO4-, m/z 97). Deuterium labeling experiments confirm that the proton transferred to oxygen during bisulfate elimination normally originates from the C-2 position, although examination of the spectra of polyfunctional steroids reveals that the proton abstracted may originate from more distant sites as well. Adamantyl, phenyl, and vinyl sulfate anions, which do not readily lend themselves to a cyclic syn-elimination, do not give rise to an mit 97 ion. Instead, these sulfates undergo both heterolytic and homolytic S-O bond cleavages to yield an m/z M - 80 anion, resulting from loss of neutral SO3, as well as an ion at mh 80, corresponding to SO3-., respectively. Sulfates that can give rise to a resonance stabilized radical by homolytic C-O bond fission, as exemplified by benzyl and linalyl sulfates, can be recognized by the formation of an m/z 96 (SO4-.) ion.