Carde, Robert N (1974) Intramolecular nitrene insertions into aromatic systems. Doctoral thesis, Keele University.

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Abstract

A study of the intramolecular insertion reactions of aryl nitrenes is described.
In Part I the preparation and photolytic decomposition of a number of aryl azides in diethylamine is described. The usual products were 3H-azepines but in one case ring expansion did not occur and the major product was an aryl amine. Attempts to prepare aza-azulenes and azepinium salts from certain of the decomposition products were unsuccessful.
In Part II an account of the experiments used to determine the effect of annelation upon the nitrene insertion reaction is given. The decomposition of 1- and 2-(azidobenzyl)naphthalene was shown to give predominantly acridan and acridine products, while the tetrahydro derivatives, 5- and 6-(2-azidobenzyl) tetralin, gave the ring insertion products, benzazepinoindoles. The reasons for the differing reaction pathways are discussed.
In Part III the preparation and thermal decomposition
of a number of 2-azidotriphenylmethanes is described. The usual products were aoridans and azepinoindoles but in one case, when a 4'-methoxyl group was present in the azide, the major product was an 8,9-methanopyridoindole. Experiments to determine the nature of the [1,,3] hydrogen shift observed in the formation of the azepinoindoles are described. A mechanism is proposed which satisfactorily accounts for the observed products and product ratios.

Item Type: Thesis (Doctoral)
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Natural Sciences > School of Chemical and Physical Sciences
Depositing User: Lisa Bailey
Date Deposited: 05 Mar 2019 10:06
Last Modified: 05 Mar 2019 10:06
URI: http://eprints.keele.ac.uk/id/eprint/6002

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