Studies in the Azulene and Tropolone Series

Somerville, Andrew R (1950) Studies in the Azulene and Tropolone Series. PhD thesis, University of Glasgow.

Abstract

A new synthesis of azulene is described. Suberone is condensed with diethyl succinate, the product (XXIII) cyclised and the resulting keto-ester hydrolysed and decar-boxylated to 1-keto-octahydroazulene (XXIV). This has been reduced by aluminium isopropoxide to the corresponding carbinol, and by the Clemmensen method, after hydrogenation of the double bond, to deoahydroazulene. These products have been dehydrogenated to give azulene in small yields. The synthesis of 1-phenylazolene from the ketone XXIV was attempted, but has not been successful. A similar condensation of 2:3-benzo suberone with diethyl succinate followed by cyclisation etc. led to 1-ketohexahydrobenzazulene (XXXII) which has been reduced by various means, but dehydrogenation of the reduction products to 4:5-benzazulene has not been accomplished. 2-Methyl-6-carbethoxyazulene has been prepared by treatment of 2-methyl indane with diazoacetic ester and dehydrogenation of the product. This has been hydrolysed to the free acid, ammonolysed to the amide, and reduced with lithium aluminium hydride to 2-methyl-6-hydroxymethyl-azulene. Attempts at Hofmann degradation or lithium aluminium hydride reduction of the amide, in order to obtain amines, were unsuccessful.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1950
• Depositing User: Enlighten Team
• Unique ID: glathesis:1950-79821
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 03 Mar 2020 10:33
• Last Modified: 03 Mar 2020 10:33
• URI: https://theses.gla.ac.uk/id/eprint/79821