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Title: Investigations of the synthesis of new photochromic oxazine and oxadiazine derivatives
Author: Rowe, David Martin
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1996
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This thesis is concerned with the investigation of new synthetic routes to novel oxazine and oxadiazine derivatives which are of potential photochromic importance. A general synthetic strategy for the synthesis of 2,2-disubstituted 2H-benz-1,4-oxazines based on the synthesis of 2-nitrophenoxyacetaldehydes and their reductive cyclisation via a situ ring closure of intermediate 2-aminophenoxyacetaldehydes was investigated. Various attempts having failed to achieve the reductive cyclisation of the 2-nitrophenoxyacetaldehydes to the 2H-benz-1,4-oxazines, attention was turned to an alternative approach to the 2-aminophenoxyacetaldehydes involved as the incipient intermediates. This approach is based on the formation and subsequent hydrolysis of 2-formamidophenoxyacetaldehydes and successfully afforded 2,2-disubstituted 2H-benz-1,4-oxazines. The chemistry of the benz-1,4-oxazines was investigated and they were found to behave as cyclic imines. Expansion of this chemistry has led to the formation of 3-cyano-2H-benz-1,4-oxazines. The synthesis of 2,2-disubstituted 3,4-dihydro-2H-benzoxazin-3(4H)-ones as possible synthetic precursors of the 2,2-disubstituted 2H-benz-1,4-oxazines was also briefly examined. Attempted application of the aforementioned methodologies to the synthesis of naphth-1,4-oxazine derivatives was largely unsuccessful. Alkali metal salts of 1-nitoso-2-naphthol were preformed and isolated. Reaction of these salts with 2-bromo-2,2-diphenylacetaldehyde afforded naphthalene-1,2-dione-1-oxime diphenylformylmethyl ether. Reduction of this oxime ether with triphenylphosphine afforded 3,3-diphenyl-3H-naphth[2,1-b]-1,4-oxazine. Similarly 2,2-diphenyl-2H-naphth[1,2-b]-1, 4-oxazine was prepared in a parallel synthetic sequence using 2-nitroso-1-naphthol as the key starting material.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available