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Mechanism of Formation of Heterocyclic Compounds by Reaction of Hydrazoic Acid with Cyclic Compounds: Synthesis of Benzoxazines.

Marks, Robert Edward. (1957) Mechanism of Formation of Heterocyclic Compounds by Reaction of Hydrazoic Acid with Cyclic Compounds: Synthesis of Benzoxazines. Doctoral thesis, University of Surrey (United Kingdom)..

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Abstract

2-a-Naphthoyl- , 2-p-methoxybenzoyl-, 2-p-chlorobenzoyl-, 2-m-nitrobenzoyl-, 2-mesitoyl-, 2-phenylacetyl-, and 2-butyryl-benzoic acids, and benzylidene- and propylidene-phthalides have been subjected to the conditions of the Schmidt reaction to yield, principally, 2-substituted-6-oxo-4:5-benz-1:3-oxazines. Where the substituent is aryl the oxazine can be isolated under the conditions employed; 2-p-methoxyphenyl-, 2-p-chlorophenyl-, 2-m-nitrophenyl-, 2-a-naphthyl, and 2-mesityl-6-oxo-4:5-benz-1:3-oxazines were so obtained. Where the substituent is alkyl or aralkyl the hydrolysis product, an N-substituted-anthranilic acid, is isolated; N-phenylacetyl-and N-butyryl-anthranilic acids were obtained. The mechanism of this reaction, believed to proceed via a cyclic ion, is discussed. Evidence for the existence of a counter-rearrangement, which leads, not to a 2-substituted-6-oxo-4:5-benz-1:3-oxazine or an N-substituted-anthranilic acid, but ultimately, to a primary amine, is given, and the mechanism of the counter-rearrangment is discussed. Experiments concerning the Schmidt reaction of 1:2-benzofluorenone are described. The preparation of 1:2- and 7:8-benzophenanthridines from 9-azido-1:2 -benzofluorene is recorded; the ratio of isomers, 2. 9: 1, is shewn to be in accord with views based on earlier work in the field. A novel method for the preparation of certain 9-azidofluorenes is described. New observations on the acid-catalysed decomposition and the pyrolysis of 9-azido-fluorenes, together with data in the literature, lead to the conclusion that acid-catalysed decomposition of secondary and tertiary azides, also pyrolysis of the latter, yield substituted phenanthridines, but that pyrolysis of secondary azides yields ketimines. The preparation of 2:4-dihydroxyquinoline from 1:3-diketohydrindene, via the Schmidt reaction, has been verified.

Item Type: Thesis (Doctoral)
Divisions : Theses
Authors :
NameEmailORCID
Marks, Robert Edward.
Date : 1957
Contributors :
ContributionNameEmailORCID
http://www.loc.gov/loc.terms/relators/THS
Additional Information : Thesis (Ph.D.)--University of Surrey (United Kingdom), 1957.
Depositing User : EPrints Services
Date Deposited : 22 Jun 2018 15:15
Last Modified : 06 Nov 2018 16:54
URI: http://epubs.surrey.ac.uk/id/eprint/848279

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