Initial studies were based on previous work at Edinburgh in which the reaction of the lithium salt of 1,2-naphthalenedione 1-oxime with 2-bromo-2,2-diphenylacetaldehyde was found to afford an oxime ether which was reduced with triphenylphosphine to afford 3,3-diphenyl-3<i>H</i>-naphth[2,1-<i>b</i>]-1, 4-oxazine. Similarly, 2,2-diphenyl-2<i>H</i>-naphth[1,2-<i>b</i>]-1,4-oxazine was prepared in a parallel synthetic strategy using 1,2-naphthalenedione 2-oxime as key starting material. To facilitate the expansion of this strategy, further bromo-aldehydes functionalised with variously substituted aromatic moieties were prepared. Reaction of these bromo-aldehydes with 1,2-naphthalenedione 1-oxime lithium salt, followed by reduction of the resulting oxime ethers, facilitated the synthesis of a number of novel 3,3-diaryl-3<i>H</i>-naphth[2,1-<i>b</i>]-1,4-oxazine derivatives. On encountering problems in the synthesis of certain diaryl bromo-aldehydes, the synthesis of alternative diarylacetaldehyde derivatives amenable to reaction with naphthalenedione oxime lithium salts was previously inaccessible halogeno-aldehydes was investigated. Using 1,2-naphthalenedione 2-oxime and 9, 10-phenanthrenedione 9-oxime as starting materials the aforementioned methodologies were applied to the respective syntheses of 2,2-diaryl-2<i>H -</i>naphth[1,2-<i>b</i>]-1,4-oxazines and 2,2-diaryl-2<i>H</i>-phenanthro[9,10-<i>b</i>]-1,4-oxazines. Investigations were also made into the mechanism of the formation of these novel photochromic species. The chemistry of certain novel naphth-1, 4-oxazines and phenanthro-1, 4-oxazines was investigated and they were found to behave as cyclic imines. Photochromic 3,3-diaryl-3<i>H</i>-pyrido[3,2-<i>f</i>]-1, 4-benzoxazines were also prepared. However, the attempted synthesis of 2,2-diphenyl-2<i>H</i>-acenaphtho[1,2-<i>b</i>]-1, 4-oxazine was unsuccessful. Work was also undertaken on various synthetic routes to diarylnaphth-1, 3-oxazine derivatives. Initial attempts were based on the preparation and cyclisation of 1-benzoylaminomethyl-2-naphthol. This having failed, an alternative approach involving the reaction of diarylketimines with 2-hydroxy-1-naphthaledhyde was investigated and successfully afforded 3,3-diaryl-3<i>H</i>-naphth[1,2-<i>e</i>]-1, 3-oxazines. In parallel with these studies the analogous syntheses of 2,2-diphenyl-2<i>H</i>-naphth[2,1-<i>e</i>]-1, 3-oxazine and 2,2-diaryl-2<i>H</i>-phenanthro[9,10-<i>e</i>]-1, 3-oxazines were also achieved.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:660777 |
| Date | January 2000 |
| Creators | Pritchard, Martin David |
| Publisher | University of Edinburgh |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://hdl.handle.net/1842/11283 |
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