Use this URL to cite or link to this record in EThOS: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.751373
Title: Nitrene-induced aromatic rearrangements
Author: Kulik, Stanley
Awarding Body: University of St Andrews
Current Institution: University of St Andrews
Date of Award: 1970
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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.
Supervisor: Cadogan, John Ivan George Sponsor: Science Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.751373  DOI: Not available
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