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Nitrene-induced aromatic rearrangements
|dc.contributor.advisor||Cadogan, J. I. G. (John Ivan George)|
|dc.description.abstract||It has been shown in this investigation that thermal decomposition of mono-substitutedaryl 2-azidophenyl sulphides and deoxygenation of mono-substitutedaryl 2-nitrophenyl sulphides both proceed via a re-arrangement involving five-membered ring attack of the first-formed nitrene followed by a sigmatropic sulphur shift to give the corresponding phenothiazines. By using deuterium labelling, it has been further shown that the rearrangement occurs even in the unsubstituted 2-nitrophenyl phenyl sulphide. Decomposition of 2,6-disubatitutedaryl 2-azidophenyl sulphides and deoxygenation of 2,6-disubstitutedaryl 2-nitrophenyl sulphides led to some very interesting chemistry. For example, 2,6-dimethyl-phenyl 2-azidophenyl sulphide and 2,6-dimethylphenyl 2-nitrophenyl sulphide gave 5,11-dihydro-4-methyldibenzo[b,e][1,4] thiazepine rather than the isomeric 10,11-dihydro-4-methyldibenzo[b,f][1,i4] thiazepine, while 2,6-dimethoxyphenyl 2-azidophenyl sulphide and 2,6-dimethoxy-phenyl 2-nitrophenyl sulphide both gave 1-methoxyphenothiazine and 1,2-dimethoxyphenothiazine via a rearrangement involving a novel l,4-methoxyl shift. That these and the other examples described herein may be explained by a mechanism analogous to that postulated for the phenothiazine rearrangement was shown by the isolation of 1,4a-dicarbethoxy-4H-phenothiazine, a product analogous to the intermediate postulated, from the deoxygenation of 2,6-dicarbethoxy-phenyl 2-nitrophenyl sulphide.||en_US|
|dc.publisher||University of St Andrews|
|dc.title||Nitrene-induced aromatic rearrangements||en_US|
|dc.contributor.sponsor||Science Research Council (Great Britain)||en_US|
|dc.type.qualificationname||PhD Doctor of Philosophy||en_US|
|dc.publisher.institution||The University of St Andrews||en_US|
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