The Synthesis Analysis and Application of Tritiated Compounds.

Abstract

As the title suggests this thesis is concerned with the synthesis of tritiated compounds and their subsequent use in addressing various problems in physical-organic chemistry. Hence in chapter one the stereoselectivity shown by the base-catalysed ionisation of the C10 axial and equatorial hydrogens of a tetracyclic drug,Mianserin,for a wide range of highly basic DMSO-H[2]O-OH solutions, was investigated by using tritium as a hydrogen-tracer to determine the kinetics of this reaction. The stereoselectivity is discussed in terms of the stereochemical relationship between the axial C10 hydrogen and the lone-pair of electrons of the N5 atom. The effect of high-basicity on transition-state geometry and the stereoselectivity is also discussed. Similar tracer techniques were employed in chapter two to study the conformational effects of small to medium sized alicyclic rings on the base-catalysed ionisation of a series of methylcycloalkylketones under aqueous base conditions. The nature of the reaction intermediate is discussed in terms of the observed kinetic behaviour. Chapter three represents a complete departure from the kinetic theme of the previous chapters in that it is concerned with the isolation and tritiation of chrysophanolanthrone a natural product suspected to possess valuable pharmaceutical properties