Preparation of tartaric acid modified Raney nickel catalysts: study of modification procedure

Chiral modification of Raney nickel using (2R,3R)-tartaric acid was studied. The prepared catalyst was used in enantioselective hydrogenation of methylacetoacetate (MAA) to methyl-(3R)-hydroxybutyrate. The influence of the most important modification parameters, such as pH, temperature, time, concentration of the modifier and the presence of a co-modifier, on the optical yield of MAA hydrogenation was systematically investigated. From the data obtained: a considerable influence of modifying conditions on the resulting enantioselectivity of the catalyst was evident. The optical yield increased with an increasing of the modifying temperature and time. Dependencies of the optical yield on the tartaric acid concentration and on the modifying pH passed through a maximum. Therefore, there exists an optimal value of modifying pH, at which a minimal catalyst amount is leached to the modifying solution. Furthermore, significant adsorption of tartaric acid and subsequent complex formation of nickel and tartaric acid occurs on the catalyst surface. It was found that the presence of sodium bromide in the modifying solution resulted in a lower degree of the nickel leaching, and a decrease of the residual aluminum content in the catalyst increased the optical yield of the reaction. (C) 2001 Elsevier Science B.V. All rights reserved.