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The Application of Optical Activity to the Study of Some Reaction Mechanisms.

Young, Donald P. (1940) The Application of Optical Activity to the Study of Some Reaction Mechanisms. Doctoral thesis, University of Surrey (United Kingdom)..

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Abstract

An account is given of the known stereochemical effects of various types of reactions. (+)y-Heptyl methyl ketone has been prepared. Its oxime undergoes Beckmann rearrangement to (-)aceto-y-heptylamide with high retention of asymmetry. This is considered to afford proof that the Beckmann change is an intramolecular process. It is shown that, in all cases for which data exist, an asymmetric migrating radical . Cabe does not undergo a Walden inversion, whatever its electronic nature, Optically active disubstituted acetic esters are readily racemised by sodium ethoxide. It is submitted that this phenomenon demonstrates the existence of an equilibrium. RR'CH. COOEt + OEt- RR'C. CO. OEt + EtOH thereby affording support for mechanisms for Claisen's condensation of the type proposed by Nef. d-Methyl-d-penten-B-ol has been prepared and resolved into its optical isomers, and is proved to be identical with an alcohol previously described in error as the y -isomer (Duveen and Kenyon, J.C.S. 1936. 1451). Addition of bromine to this alcohol does not, in contrast to y-penten-B-ol (Kenyon and Partridge, ib. 1313) lead to an asymmetric synthesis. Asymmetric addition to a double bond is discussed in the light of the electronic theory. The action of formic acid on its hydrogen phthalic ester leads to addition of the elements of water to the ethylenic bond. The true d-methyl-y-penten-B has been prepared. Reduction of mesityl oxide yields this alcohol containing a little d-compound, believed to have arisen from an isomer, CH2:CMe. CH2. COMe in ordinary mesityl oxide. On catalytic dehydration it sometimes abnormally gives ay-butadiene. Its eaters with electron-attractive acyl groups are unstable. The chemical properties of these compounds are compared with those of other substituted allyl alcohols. 1-B-Octyl nitrite interacts with dl-B-butanol to give dl-B-butyl nitrite and 1-B-octanol. No further light is cast on the postulated formation of an addition complex in this interchange.

Item Type: Thesis (Doctoral)
Divisions : Theses
Authors : Young, Donald P.
Date : 1940
Additional Information : Thesis (Ph.D.)--University of Surrey (United Kingdom), 1940.
Depositing User : EPrints Services
Date Deposited : 22 Jun 2018 15:16
Last Modified : 06 Jul 2019 05:25
URI: http://epubs.surrey.ac.uk/id/eprint/848404

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