Syntheses Employing Acetylenic Compounds

Roxburgh, Charles M (1955) Syntheses Employing Acetylenic Compounds. PhD thesis, University of Glasgow.

Abstract

Many of the varied reactions of acetylenic compounds have been well established for a number of years, and in recent times their utilisation in solving problems of organic synthesis has attracted attention. Successful and elegant work has resulted in many fields. In the present research, the application of the peculiar properties of the triple bond has been sought in the synthesis of compounds in the field of carbohydrates, including two natural products. A meso-dideoxyhexitol, erythro-hexane-1:3:4:6-tetrol, has been synthesised from acetylene by an unambiguous method, and was not identical with the compound to which this constitution has hitherto been ascribed. The latter compound had arisen from an unexpected variant of the standard reaction, carbonyl reduction by Raney nickel hydrogenolysis of the acetylated sugar thioacetal, when applied to keto-D-psicose penta-acetate. Two unusual pentoses have been synthesised. These compounds, apiose and cordycepose, are members of the small group of natural sugars having a branched carbon chain. several promising synthetic approaches to apiose and cordycepose, some of which were based on acetylenic intermediates, have been investigated and found to be impracticable. In the case of each sugar, the route that was eventually developed into a successful and smooth synthesis starts from the condensation of bromoacetal and ethyl malonate. The structures indicated by degradative evidence for apiose and cordycepose are thereby confirmed.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1955
• Depositing User: Enlighten Team
• Unique ID: glathesis:1955-79163
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 05 Mar 2020 11:36
• Last Modified: 05 Mar 2020 11:36
• URI: https://theses.gla.ac.uk/id/eprint/79163