Premium
A mass spectral study of the acid‐catalysed oxygen exchange in laevulinic acid
Author(s) -
Srzić D.,
Horvat J.,
Šunjić V.,
Kralj B.
Publication year - 1988
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.1210231207
Subject(s) - chemistry , fragmentation (computing) , mass spectrometry , tautomer , ion , oxygen , mass spectrum , reaction mechanism , kinetic energy , spectroscopy , ion exchange , stereochemistry , medicinal chemistry , analytical chemistry (journal) , catalysis , organic chemistry , chromatography , physics , quantum mechanics , computer science , operating system
The sequence, i.e. site selectivity of the acid‐catalysed 16 O/ 18 O exchange in laevulinic acid (1) is studied by mass spectrometry, ion kinetic energy spectroscopy and accurate mass measurements on 1 and its 13 C(1)‐labelled congener. In the fragmentation pathways all ions of interest in the spectrum of 1 originate from the molecular ion, which may exist in six tautomeric or isomeric forms (1a–1d). The mechanism of gas‐phase cyclization of 1a is rationalized in terms of three different pathways. Formation of the most prominent fragment ions and the sequence of 16 O/ 18 O exchange at the carbonyl and carboxy group are discussed. The results indicate the ions of m / z 56, m / z 61 and m / z 98 to be the only three which have incorporated oxygen atoms originating from the carboxy group in 1 and could thus be used in further elucidadon of the rearrangement mechanism of 5‐hydroxymethylfuran (2) or 5‐hydroxymethylfuran‐2‐carbaldehyde (3) into laevulinic acid (1).