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The study and characterization of nucleosides by mass spectrometry—I: The mass spectra of pyrimidine 2,2′‐anhydronucleosides and their derivatives
Author(s) -
Westmore J. B.,
Lin Denis C. K.,
Ogilvie K. K.,
Wayborn H.,
Berestiansky J.
Publication year - 1972
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210061110
Subject(s) - chemistry , trimethylsilyl , mass spectrum , moiety , ring (chemistry) , molecule , mass spectrometry , medicinal chemistry , hydrogen atom , fast atom bombardment , deuterium , hydrogen , pyrimidine , polyatomic ion , ion , stereochemistry , organic chemistry , group (periodic table) , physics , chromatography , quantum mechanics
The mass spectra of 2,2′‐anhydrouridine, 2,2′‐anhydrothymidine and 2,2′‐anhydro‐4‐thiouridine are reported. The acetyl, trifluoroacetyl, trityl, pivaloyl and trimethylsilyl ether derivatives were also studied. Deuterium labeling in acetyl and trimethylsilyl groups aided characterization of many ions in the spectra, as well as helping to clarify hydrogen migration processes. The anhydronucleosides and their derivatives are readily distinguished from natural nucleosides by the presence of an ion containing the base moiety plus the anhydro‐ring plus one hydrogen atom from the rest of the molecule. As for natural nucleosides the [base + H] + and [base + 2H] + ions are usually prominent, but in contrast to natural nucleosides, ions characteristic of the sugar moiety do not retain the 2′‐oxygen atom (i.e. the oxygen atom of the anhydro‐ring). The mass spectra of deuterium labeled derivatives suggest a test for the presence of a 3′‐O‐acetyl function (the O‐acetyl group is lost from the molecular ion much more readily from the 3′‐ than from the 5′‐carbon atom). The trimethylsilyl derivatives showed evidence in their mass spectra for migration of trimethylsilyl groups in addition to hydrogen atoms.