New Directions in the Chemistry of Azo-compounds

Abstract

The synthesis and chemical reactivity of azo-dyes is reviewed and their application to the field of molecular sensors is outlined. The main body of the thesis is concerned with the development of synthetic strategies for the construction of sensing agents which are of potential value in the diagnosis of metal-dependent neurodegenerative diseases. The functionalisation of readily available azo-dyes is described including the use of Heck, Stille reactions and the application of a novel benzannulation reaction to the synthesis of benzo-fused azo-dyes. During these investigations an unprecedented redox-cyclisation reaction of naphthol-derived azo dyes was discovered, leading to the synthesis of the previously unknown 2,3-dihydro-1H-naphtho[1,2-e][1,3,4]oxadiazine ring system. These novel heterocycles were fully characterised by spectroscopic and X-ray diffraction techniques. The development of an Ullmann-type displacement reaction of halo substituted azo-dyes is also reported. This process will enable the conjugation of azo-dyes to macrocyclic systems and provides a modular approach to the synthesis of macrocycles capable of sensing heavy metals in biological systems.

Date of Award	3 Jan 2012
Original language	English
Awarding Institution	The University of Manchester
Supervisor	Peter Quayle (Supervisor)