Abstract:Electron impact mass spectra of eight of the title compounds are reported. Abundant fragment ions were produced under electron impact (EI) conditions and, with one exception, the ($¿hbox¿ArC¿¿equiv$ O) ions were the base peaks. The EI fragmentation mechanisms of two representative compounds were studied with the aid of high-resolution and mass-analyzed ion kinetic energy spectrometry (MIKES) data. The M(+) ions fragment to give both an odd-electron ion and an even-electron fragment ion. Two H-atom rearrangemen… Show more
“…The fragmentation pathway proposed to form ion 1c is rather complex. It includes a four‐membered ring H‐rearrangement followed by α‐cleavage, radical site transfer, and another four‐membered ring H‐rearrangement followed by i‐cleavage 4–6. This process is shown in Scheme .…”
A series of cyclic esters, which are optically active as a consequence of their helical structures, were synthesized to investigate the relationships between their structures and their optical activities. This paper reports the electron impact fragmentation mechanisms of these six cyclic esters. Accurate mass measurements and mass analyzed ion kinetic energy spectrometry confirmed fragmentation patterns. The stability of the fragment ions has a great influence on the fragmentation pathways, but no correlation with the optical activity was found.
“…The fragmentation pathway proposed to form ion 1c is rather complex. It includes a four‐membered ring H‐rearrangement followed by α‐cleavage, radical site transfer, and another four‐membered ring H‐rearrangement followed by i‐cleavage 4–6. This process is shown in Scheme .…”
A series of cyclic esters, which are optically active as a consequence of their helical structures, were synthesized to investigate the relationships between their structures and their optical activities. This paper reports the electron impact fragmentation mechanisms of these six cyclic esters. Accurate mass measurements and mass analyzed ion kinetic energy spectrometry confirmed fragmentation patterns. The stability of the fragment ions has a great influence on the fragmentation pathways, but no correlation with the optical activity was found.
A combination of accurate mass measurement and tandem mass spectrometry (both product ion and precursor ion scans) have been used to characterize the major fragment ions observed in the ESI mass spectrum of kynurenine. Kynurenine is a metabolite of tryptophan found in the human lens and is thought to play a role in protecting the retina from UV-induced damage. Three major fragmentation pathways were evident, following initial elimination either of ammonia, H2O and CO or the imine form of glycine. The latter is proposed to occur via the formation of an ion-molecule complex. In the case of loss of H2O and CO from deaminated kynurenine, there is evidence for an acylium ion intermediate, which is not observed for the loss of H2O and CO directly from protonated kynurenine. Product ion scans of deuterated kynurenine enabled the elucidation of structural rearrangements that were not evident in the spectra of the native compound. Since UV filter compounds can often only be isolated in small quantities from the lens, this study forms the basis for the characterization of novel UV filter compounds using mass spectrometry. The approach presented here may also be useful for the characterization of related classes of small molecules.
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