Some Kinetic Studies on Ketone Formation

Thornley, Margaret Bennett (1956) Some Kinetic Studies on Ketone Formation. PhD thesis, University of Glasgow.

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The thesis consists of two parts. In the first, a kinetic study was made of the Dieckmann ring closure of alpha- and beta-alkyl-substituted esters of adipic acid. This may be considered as an intramolecular Claisen condensation, where the accepting carbonyl centre is influenced by the alkyl substituent R, while the attacking centre is nonsubstituted. The reaction has been studied for +I substituents, which, according to current theories, should decelerate nucleophilic substitution. A reaction mechanism has been proposed, which requires that the rate determining process is the making or breaking of the relevant carbonyl carbon-carbon bond, or, regarding this reaction as a typical carbonyl addition, the slow step is the union of the anion produced by base extraction, with the carbonyl group. Part two is a kinetic study of the pyrolytic decomposition of sodium salts of adipic acid, beta-methyl-adipic acid and acetic acid. The results show that the order of reaction in each case is integral, which indicates that the mechanism is ionic rather than free radical. The decomposition of disodium adipate, has been considered to he an autocatalytic reaction of the first order, while that of beta-methyladipic acid is unimolecular. Pyrolysis of sodium acetate to yield acetone, however is more complicated. For about 50% of its course, the pyrolysis obeys a second order rate equation, but as the reaction proceeds further, the order becomes complex. It was also noted that at higher temperatures - above 480

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Organic chemistry
Date of Award: 1956
Depositing User: Enlighten Team
Unique ID: glathesis:1956-79175
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 05 Mar 2020 11:34
Last Modified: 05 Mar 2020 11:34

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