Browse DORAS
Browse Theses
Search
Latest Additions
Creative Commons License
Except where otherwise noted, content on this site is licensed for use under a:

The photo-Friedel-Crafts acylation of naphthoquinone in alternative “green” media and the photochemical generation of novel biaryl trifluoro phthalonitriles, their condensation to phthalocyanines and evaluation as singlet oxygen sensitisers

Murphy, Brian (2012) The photo-Friedel-Crafts acylation of naphthoquinone in alternative “green” media and the photochemical generation of novel biaryl trifluoro phthalonitriles, their condensation to phthalocyanines and evaluation as singlet oxygen sensitisers. PhD thesis, Dublin City University.

Full text available as:

[img]PDF - Archive staff only. This file is embargoed until 19 September 2015 - Requires a PDF viewer such as GSview, Xpdf or Adobe Acrobat Reader
2942Kb

Abstract

The aim of this research was to investigate the photo-Friedel-Crafts acylation of napthoquinone with a variety of aldehydes using a Rayonet reactor. The long-term aim of this project was to apply this research to the synthesis of biologically active natural products such as alkannin and shikonin. As a 100% atom efficient, solar reaction, the photo-Friedel-Crafts acylation of naphthoquinone is understood to be a very environmentally friendly reaction. With this in mind, it was undertaken to improve the “green” nature of this reaction by replacing harmful traditional solvents such as benzene with more benign alternatives. Ionic liquids were chosen for this purpose, due to their low vapour pressure, recyclability, low flammability and customisable solubilising and catalytic properties, as well as the fact that they have been shown to stabilise reactions with radical intermediates. The reaction was also performed in microemulsions. As an extension of previous work done in DCU by Pratt et al. it was undertaken photochemically generate a series of biaryl trifluorophthalonitriles, and optimise the reaction conditions necessary for their synthesis. Once these novel phthalonitriles had been generated a method for condensing them to phthalocyanines was developed. The novel phthalocyanines generated using this method were then assessed as catalysts for photooxygenation reactions. It was hoped that the introduction of peripheral aryl groups would increase the solubility of the phthalocyanines as well as reducing aggregation.

Item Type:Thesis (PhD)
Date of Award:November 2012
Refereed:No
Supervisor(s):Nolan, Kieran and Oelgemöller, Michael
Uncontrolled Keywords:phthalonitrile; phthalocyanine; photooxygenation
Subjects:Physical Sciences > Photochemistry
Physical Sciences > Organic chemistry
DCU Faculties and Centres:DCU Faculties and Schools > Faculty of Science and Health > School of Chemical Sciences
Use License:This item is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 3.0 License. View License
ID Code:17510
Deposited On:26 Nov 2012 16:31 by Kieran Nolan. Last Modified 26 Nov 2012 16:31

Archive Staff Only: edit this record