The formation of phenanthridines, and other heterocyclic compounds, by the reaction of hydrazoic acid with cyclic compounds. The mechanism of such reactions.

Coombs, M. M. (1954) The formation of phenanthridines, and other heterocyclic compounds, by the reaction of hydrazoic acid with cyclic compounds. The mechanism of such reactions. Doctoral thesis, University of Surrey (United Kingdom)..

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Abstract

Eleven fluoren-9-ols, monosubstituted at positions 2,3, or 9, have been submitted to reaction with hydrazoic acid in the presence of sulphuric acid, and the following have been obtained: 2-,3-,6-, and 7-nitro, 7-amino-, 2- and 7-methoxy-,2-,3-,7, and 9-methyl, 9-phenyl, and 9-bensylphenanthridines. The last is also obtained by the action of hydrasoic and sulphuric acids upon 9-benzylidenefluorene. The pairs of isomeric phenenthridines from the unsymmetrically substituted from the unsymmetrically substituted fluorenola have been separated and the product ratios have been determined. It is found that the ratio of 3- and 7-methoxyphenanthridines from the reaction with 2-methoxyfluoron-9-ol is the same as that from the acid catalyzed decomposition of 9-azido-2-methoxyfluorene. It is demonstrated that the above results support a reaction mechanism in which the carbonium ion derived from the fluorenol adds hydrazoic acid to form the protonated azide which undergoes intramolecular rearrangement, the case of migration of the substituted and unsubstituted rings being directly related to their especity for electron release at the migration origin. Reactions of phonanthridine 6- and 7-diazonium sulphates, and of 7-hydroxyphonanthridine are reported, and new syntheses of 2- and 3-nitrophonanthridines and 2:7-dinitrophonanthridine have been carried out. The Schmidt reaction with three unsymmetrically substituted fluorences has been investigated. The literature of the Schmidt reaction with ket ones has been surveyed critically, and a new proposal concerning the observed "geometrical effect" has been made. The Schmidt reaction with 2-p-toluoylbenzoic acid has been found to yield 6-oxo-2-p-tolyl-4:5-bone-1:3-oxazine: the mechanism of this reaction is discussed.

Item Type:	Thesis (Doctoral)
Divisions :	Theses
Authors :	Name Email ORCID Coombs, M. M.
Date :	1954
Contributors :	Contribution Name Email ORCID http://www.loc.gov/loc.terms/relators/THS
Depositing User :	EPrints Services
Date Deposited :	09 Nov 2017 12:18
Last Modified :	20 Jun 2018 12:00
URI:	http://epubs.surrey.ac.uk/id/eprint/844651

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