Studies in the Organic Chemistry of Sulphur Compounds

Cowie, Douglas Williamson (1935) Studies in the Organic Chemistry of Sulphur Compounds. PhD thesis, University of Glasgow.

Abstract

The original problem was the investigation of the exchange reaction (vide (3)). This thesis falls into three parts: (1) On Bisarylsulphonyl propanes. (2) The Micro-estimation of Sulphur and Halogen in Organic Compounds. (3) A Quantitative Investigation of the Exchange Reaction. The sulphonyl propanes were investigated because more of them appeared toexist than could be accounted for on the usual theories of isomerism. It was thought that the anomaly might be explained on the basis of the mobility of the sulphonyl group. It is shown below that this is not the case. Their isomerism is to be traced to quite a different cause, (vide (1)). Returning to the original problem of radical exchange it was evident that no quantitative idea of the exchange could be deduced from separating the products of the reaction as they were too similar in properties to be separated without serious loss. Accordingly it was decided to investigate the competition of two radicals containing such characteristic groups as could readily be estimated in the mixed final product. Thus if, in the above equation, 4-chlorophenyl sulphonyl acetone, reacts with methyl p.toluenethiol sulphonate the product will he either p.tolyl sulphonylmethyl-thioacetone or 4-chlorophenyl-sulphonylmethyl thioacetone or more prohahly a mixture of the two. A reaction of the above type goes practically to completion so far as the substitution of the methylthio grouping is concerned and so it is evident that an estimation of the halogen content will indicate the percentage composition of the mixed product. Accordingly the development and detailed testing of a rapid and accurate micro method for the estimation of chlorine and sulphur had to be undertaken (vide (2)).The application of this analytical procedure to the exchange reaction between 4-chlorophenylsulphonylacetone and methyl p.toluene thiolsulphonate has been worked out in detail (vide (3)).

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1935
• Depositing User: Enlighten Team
• Unique ID: glathesis:1935-80037
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 03 Mar 2020 10:04
• Last Modified: 03 Mar 2020 10:04
• URI: https://theses.gla.ac.uk/id/eprint/80037