Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.663926
Title: The reactions of diene- and triene-conjugated diazo-compounds
Author: Wilson, Paul
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1999
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Abstract:
Two series of diene-conjugated diazo-compounds, a-diazoesters and a-diazophosphonate esters, were generated. In cases where the a,b and g,d-double bonds were aromatic in character both series decomposed to give fluorene derivatives. a-Diazoesters where the a,b-bond was olefinic and the g,d-bond was part of an aromatic ring gave 3-phenyl indenes as the sole product. The structures of these products were confirmed by the synthesis of authentic compounds. a-Diazophosphonate esters where the a,b-double bond was part of an aromatic ring and the g,d-bond was olefinic gave a moderate yield of 5H-2,3-benzodiazepine and 2,-phenylindene. Triene-conjugated diazo-compounds with all cis stereochemistry where a cyclopentene ring was fused across the g,d-double bond, reacted via a [3+2]-cycloaddition reaction of unprecedented regioselectivity to give benzo[d]cyclopenta [1,2]diazocines. Where a cyclohexene ring was fused across the g,d-double bond the only isolated product was hexahydrocyclopropa [f]phenanthrene. Triene-conjugated diazo-compounds with a methyl and phenyl group on the g,d-double bond and possessing all cis stereochemistry reacted to give cyclopropa[a]napthalene as the major product and cyclopenta[a]phthalazine as the minor product. The cyclopenta[a]phthalazine was formed via a 1,1-cycloaddition of the diazo-compound with the g,d-double bond a reaction path unprecedented in such systems. Where the stereochemistry of the g,d-double bond is trans then the cyclopenta[a]phthalazine becomes the major product of the reaction with some of the cyclopropa[a]napthalene as the minor product.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.663926  DOI: Not available
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