Exploiting the photochemistry of the quinones

• Main Author: Mitchell, Lorna J.
• Published: University of Nottingham 2016
• Subjects: 547; QD241 Organic chemistry
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.689862

This thesis will focus on two main research areas with the aim of developing and exploring the solar photochemical reactivity of quinones. In Chapter One, a review of quinone photochemistry is presented; this includes both cycloaddition reactions and hydrogen abstraction reactions. After a review of the relevant literature, the aims of the research are outlined and placed into context. Chapter Two details the development of a green photo Friedel-Crafts acylation for the preparation of acylated hydroquinones, which serve as versatile precursors for the synthesis of numerous biologically active quinone natural products. After a review of the relevant literature, the results of the research are discussed. Key achievements include the development of an accessible and ‘greener’ synthetic protocol employing a ‘sun-mimicking’ light source and trifluorotoluene as solvent. The factors influencing the regiochemical outcome of the acylation are also discussed. In Chapter Three, the photochemical oxidising ability of p-benzoquinone in both stoichiometric and substoichiometric quantities is investigated. In the introduction, a short review of the oxidising ability of the quinones - particularly DDQ - is presented and the enhanced oxidising ability of p-benzoquinone upon irradiation is discussed. The potential breadth of this underexploited oxidising ability is then investigated in the use of alcohol oxidation and C-H functionalisation protocols. Chapter Four summarises the results obtained in the thesis and outlines scope for further research in the area. In Chapter Five, full experimental details for the research are presented.