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Title: The hydrolysis of diortho-substituted benzoates : the separation of optically pure amyl alcohol from fuel oil and the study of some of its oxidation products
Author: Le Couteur, Peter
Awarding Body: University of Surrey
Current Institution: University of Surrey
Date of Award: 1950
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Part I. The Hydrolysis of Diortho-Substituted Benzoates. In order to define more clearly the conditions under which the different mechanisms for hydrolysis apply to esters of diortho-substituted benzoic acids a study of the hydrolysis of methyl, n-butyl, y-butyl, (+)B-octyl 2.4.6. trimethyl-benzoates and y-butyl 2.6. xylate by acids and alkalis, under varying conditions, has been made. Though these esters were found to be very resistant to alkaline hydrolysis it was, however, shown that diortho-substituted benzoates, from an alcohol possessing a strong ability to release electrons (e.g. y-butyl alcohol), can be somewhat easily hydrolysed in acid solutions. The evidence for assuming that a bimolec-ular mechanism is operative in the former case and a unimolecular mechanism in the latter is reviewed. Other factors effecting hydrolysis, e.g. acid catalysis, ionising power of the solvent, Ionic Strength effect, Mass-Law effect, and structure of the acid radical are discussed. Part II. The Separation of Optically Pure Amyl Alcohol from Fusel Oil and the Study of some of its Oxidation Products. The separation of optically pure (-)sec-butyl carbinol from fusel oil, by fractional distillation in relatively simple equipment, is for the first time described and the superiority of this method over that used previously by Marckwald and Mc Kenzie, i. e. repeated crystallisation of amyl hydrogen 3-nitrophthalate, is shown. The oxidation of (-) sec-butyl carbinol to (+) valeraldehyde and (+) methyl -ethyl acetic acid is discussed and explanations put forward for the racemisation which takes place during the preparation and reactions of (+)valeraldehyde. The oxidation of (-)sec-butyl carbinol direct to (+)methylethyl acetic acid was found to proceed without racemisation and served to confirm the optical purity of the (-)sec-butyl carbinol. The preparation of a specimen of (+) sec-butylmethyl acetate with the highest rotatory power yet recorded is described. Finally, the principal reactions of (-)sec-butyl carbinol and its simple derivatives are summarised and their mechanisms briefly discussed.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available