Rotational barriers in heterocyclic sulphenamides: Intermolecular trapping of sulphenylnitrenes.

The first part of this work is an investigation of the reason for the abnormally high barrier to rotation around the N-N bond in certain N-quinolone substituted sulphenamides. Some mechanisms by which diastereoisomers of the above compounds could interconvert are also examined. Extension of this work lead to resolution of N-benzyl-N-(1,2-dihydro-2-oxoquinolin-1-yl) glycine as a result of the N-N chiral axis. The thermal stability of some heterocyclic sulphenamides is also investigated. A study of the reaction of some alkylhydrazines with arylsulphenyl chlorides is described and some mechanisms proposed for the fragmentation of the intermediate sulphenylhydrazides. The trapping of dinitrobenzenesulphenylnitrene with alkenes and other reagents is described as well as a study of the stereospecificity of its addition to cis-l-phenylpropene. The generation and attempted trapping of other sulphenylnitrenes is also investigated.