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UBC Theses and Dissertations

Hydrogenation of ∝- oximinoglutaric acid on Raney Nickel : studies toward optical resolution McGinnis, Michael J.


This thesis describes physicochemical studies to investigate a report of spontaneous optical resolution in the hydrogenation of ∝-ketoglutaric acid and its oxime by some Japanese workers in l958. Since the intention was to study the kinetics of the reaction, a rapid method for quantitative analysis of reactant and product in aqueous solution was required, and a large part of the thesis is concerned with the development of suitable analytical methods. For the reduction of the ketoacid, several methods were studied and all found unsuitable. For the production of glutamic acid from the oxime, a method using the reaction of the aminoacid with ninhydrin was quite successful. The hydrogenations were catalysed by Raney Nickel, and the work required study of the surface area of the catalyst and of its characteristics for competitive adsorption of reactant, product and phosphate buffer from the reaction mixture. The kinetic studies showed rather low reproducibility. In a number of cases, the reaction proceeded in a markedly autocatalytic manner, giving product in proportion to the square of the time. In other cases, the reaction curve was close to linear (zero-order). Except in one case which gave an optical effect of marginal significance, no spontaneous resolution was observed, neither could optical resolution be induced by doping the system with an enantiomer of the product. I conclude that autocatalytic behavior which might provide the necessary conditions for spontaneous resolution occurs in the hydrogenation, but that my results do not substantiate the Japanese workers' claim that spontaneous resolution occurs.

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