Collect. Czech. Chem. Commun. 1979, 44, 3695-3704

Catalytic activity of cupric oxide in addition reactions of alkyl cyanoacetates with 1-alkenes

Milan Hájek and Jaroslav Málek

Institute of Chemical Process Fundamentals, Czechoslovak Academy of Sciences, 165 02 Prague 6-Suchdol


In the presence of cupric oxide as the catalyst, ethyl cyanoacetate reacts with 1-alkenes to form 1 : 1 adducts in high yields. The active catalytic component was found to be a soluble copper species generated in the absence of oxygen in 10-3 to 10-5 M concentrations by a partial dissolution of cupric oxide in ethyl cyanoacetate. The homogeneous catalytic reaction proceeds already at temperatures about 80 °C at a fast rate and with high selectivity. Results of inhibition experiments in the presence of α-naphthol and galvinoxyl support strongly the view on a free-radical mechanism of the addition reaction.