Publication

Synthesis, Spectrometry, Spectroscopy and Chromatography of Aromatic Compounds

Publication Date
End of Embargo
Supervisor
Bowen, Richard D.
Keywords
Reactive mass spectrometry, Nebuliser synthesis, Electrospray, Competition experiments, Intramolecular, Intermolecular, Aromatic compounds, Quinoxalines
Rights
Creative Commons License
The University of Bradford theses are licenced under a Creative Commons Licence.
Peer-Reviewed
Open Access status
Accepted for publication
Institution
University of Bradford
Department
School of Chemistry and Biosciences. Faculty of Life Sciences
Awarded
2024
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Theses
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PhD Thesis
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Additional title
Novel Methods of Investigating the Mechanism of Condensations, Cyclisations and Related Fundamental Processes by Mass Spectrometry
Abstract
Reactive ambient mass spectrometry has been combined with competition experiments to develop a novel methodology for investigating the mechanisms and relative rates of organic synthesis. This approach has been applied to intermolecular reactions in the generation of quinoxalines and has confirmed that the mechanism operating under reactive ESI conditions is the same as that operating in the classical bulk synthesis: the phenylenediamine acts as a nucleophile and the benzil as an electrophile. The Hammett equation has also been applied to the quinoxaline system to develop a novel understanding of the effect of substitution on the rate of reaction in both the phenylenediamine and benzil components in accelerated microdroplet synthesis. Competition experiments have also been applied to intramolecular reactions of isolated ions within a mass spectrometer. Useful mechanistic information has been obtained in the fragmentations of four classes of ionised compounds, benzophenones, dibenzylideneacetones, benzanilides and cinnamamides. This new approach has given high quality, reproducible data in all cases, and provided valuable insights into the mechanisms of these ionised compounds. In summary, mass spectrometry has been used in a novel way in conjunction with competition experiments to probe in greater depth the mechanisms by which neutral and ionised species react.
URI
https://bradscholars.brad.ac.uk/handle/10454/20665
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Type
Thesis
Qualification name
PhD
Notes