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Title: Dissociation reactions of secondary alcohols, with special reference to those involving alkyl-oxygen fission in β-naphthylmethylcarbinol and substituted benzhydrols
Author: Searle, Charles Edmund
Awarding Body: University of Surrey
Current Institution: University of Surrey
Date of Award: 1948
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Dissociation reactions of secondary alcohols, with special reference to these involving alkyl-oxygen fission in beta-naphthylmethylcarbinol and substituted benzhydrols' The mechanisms of hydrolysis of alkyl halides and of carboxylie esters are discussed. A series of experiments is described which demonstrates that in solutions of pH greater than 11.75 optically active beta-naphthylmethylearbinyl hydrogen phthalate is hydrolysed with almost complete retention of asymmetry, whereas in more weakly alkaline solutions a considerable degree of racemisation occurs, due to alkyl-oxygen fission of the ester. Other reactions which involve the beta-naphthylmethylcarbinyl cation have been carried out. Some suitably substituted benzhydrols, in particular p-methoxybenzhydrol, tend to form carbonium cations under conditions similar to these whereby triphenylcarbinol is ionised: for example, coloured solutions are given in anhydrous formic acid. The Baeyar and Villger titration method for estimating the basicity of carbinols has been modified and applied to some secondary alcohols, but the In acid solutions di- and tri-aryl carbinols react readily with p-thiocresel and p-toluene sulphinic acid: the resultant thioethers and sulphones have in some cases been shown to undergo rupture of the alkyl-sulphur bond in acid media. In the presence of sulphuric and formic acids, p-methoxybezhydrol has been found to polymerise: certain of the products are highly coloured and this is ascribed to carbonium salt formation.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available