| Abstract: | The copper‐catalysed hydrogenation of triglyceride oils differs from the nickel‐catalysed reaction in that copper catalysts only hydrogenate double bonds in methylene interrupted polyunsaturated fatty acid moieties. Accordingly, the copper‐catalysed reaction stops when the triglycerides present in the reaction mixture are only monounsaturated fatty acids and polyunsaturated fatty acids in which the double bonds are separated by more than one methylene group. Copper catalysts thus exhibit a very high oleic acid selectivity. This observation has been explained in the literature by assuming that copper catalysts can only catalyse the hydrogenation of conjugated polyenes and that they are also capable of catalysing the conjugation of methylene interrupted polyenes. Accordingly, the hydrogenation of linolenic acid and linoleic acid moieties starts with their conjugation which is then followed by hydrogen addition to these conjugated acids. For both reactions (conjugation and hydrogenation) the literature assumes the Horiuti‐Polanyi mechanism stipulating the addition of a hydrogen atom to a double bond as the first step. Reinterpretation of the literature data now leads to the hypothesis that the first step in the conjugation mechanism could well be the abstraction of a hydrogen atom from an allylic methylene group rather than the addition of a hydrogen atom to a doubly bonded carbon atom. A conjugated double bond system then results from the addition of a hydrogen atom to the allylic radical formed by the foregoing hydrogen abstraction. |
