Studies in Asymmetric Transformation and Asymmetric Solvent Action

Graham, Samuel Hugh (1949) Studies in Asymmetric Transformation and Asymmetric Solvent Action. PhD thesis, University of Glasgow.

Abstract

A number of compounds, which might he expected to he unstably asymmetric, have been prepared with a view to the examination of their behaviour in asymmetric solvents. 5-Substituted derivatives of N-acetyl-N-alkyl-2-amino-4'-methyl-diphenylsulphone have been shown to undergo both first and second order asymmetric transformations in ethyl d-tartrate solution, and it has been possible to compare the relative optical stabilities of these compounds , which could not have been resolved in any other way. When the 5-substituent was lacking or was transferred to the 4 position no transformations occurred. Asymmetric derivatives of N-benzoyldiphenylamine have also been shown to undergo asymmetric transformations in ethyl d-tartrate. Potentially optically active carbonyl compounds, which might have been expected to undergo asymmetric transformations via inactive tautomers, have been examined. Except in one case no evidence of such a compound undergoing an asymmetric transformation in an optically active solvent has been obtained. The conditions governing the potential asymmetry of derivatives of cyclooctatetraene are discussed and attempts to synthesise such derivatives described. Resolution of a compound owing its asymmetry to the presence of a cyclooctatetraene ring has not been achieved. 4:5-Dimethylbenzcinnoline has been shown to exhibit stereoisomerism of the 4:5-dimethylphenanthrene type, since its d-camphorsulphonate undergoes a first order transformation in chloroform solution. Dimethylbenzcinnoline itself has not been shown to undergo an asymmetric transformation in an asymmetric solvent.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1949
• Depositing User: Enlighten Team
• Unique ID: glathesis:1949-79730
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 03 Mar 2020 10:42
• Last Modified: 03 Mar 2020 10:42
• URI: https://theses.gla.ac.uk/id/eprint/79730