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Title: Synthesis using iminyls and iminoxyls
Author: Napier, R. J.
Awarding Body: University of Aberdeen
Current Institution: University of Aberdeen
Date of Award: 1982
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Chapter one reviews the literature published on iminyl radicals since their detection in 1962. The reactions of the radicals are discussed along with the various methods used for their generation. Previous work in this Department which had shown that iminyls would abstract benzylic hydrogen atoms intramolecularly was extended in the present study. It was shown that alkyl aryl methaniminyls could abstract hydrogen atoms intramolecularly from the γ-position of the alkyl chain. The alkyl radicals thus formed then cyclised onto the phenyl ring to give tetralones after hydrolysis of the intermediate imines. The mechanism of this reaction was shown to proceed via an intermediate iminium ion, i.e. a protonated iminyl. Neutral iminyl radicals do not abstract hydrogen atoms intramolecularly. This work was then further extended to a study of the formation of heterocyclic analogues of tetralone. Attention was then turned to intramolecular additions of iminyls themselves. Earlier work had shown that iminyls added intramolecularly to olefinic and aromatic systems. Attempts to add iminyls intramolecularly to an azo group gave a multitude of products. However, generation of the corresponding iminoxyls by oxidation of the oximes resulted in formation of indazoles. Consideration was also given to addition to an imino group. However, attempted preparation of the radical precursors, i.e. the oximes, resulted in the formation of quinazolines. Cyclisation of iminoxyls was further studied by attempting intramolecular addition to double bonds and arenes. In one case, cyclisation to give a phenanthridine N-oxide was observed. In general, e.s.r. data suggested that cyclisation did occur but a variety of products were formed.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available