Organic Catalysts. V. Specific Catalytic Properties of Copper-Iron-Polyphthalocyanine in the Oxidation of Aldehydes

Abstract

Abstract Copper-iron-polyphthalocyanine showed a specific catalysis for the oxidations of the substituted benzaldehydes and the saturated aldehydes with oxygen. The catalytic activity of copper-iron-polyphthalocyanine was solvent-dependent: tetrahydrofuran, ethanol, acetonitrile, ethyl acetate and anisole inhibited the oxidation of benzaldehyde by copper-iron-polyphthalocyanine and oxygen, while benzene and acetone resulted in catalytic oxidation. Benzaldehyde and the saturated aliphatic aldehydes in benzene were oxidized catalytically with copper-iron-polyphthalocyanine and oxygen to afford the corresponding peroxy acids and acids in quantitative yields. Furthermore, oxygen was absorbed with no induction period; the rate of oxygen absorption was in the range of 8–13 ml/min. On the other hand, the unsaturated aliphatic aldehydes, cinnamaldehyde and acrolein, were oxidized with a very slow rate of oxygen absorption in spite of the existence of copper-iron-polyphthalocyanine in the reaction system. p-Methylbenzaldehyde and p-chlorobenzaldehyde were oxidized by copper-iron-polyphthalocyanine and oxygen in Induction periods of about 8 and 15 min respectively, thus affording the corresponding peroxy acids and acids. However, no oxidations of p-nitrobenzaldehyde, p-hydroxycarbonylbenzaldehyde, p- and m-hydroxybenzaldehyde, p- and m-methoxybenzaldehyde and p-dimethylaminobenzaldehyde with copper-iron-polyphthalocyanine and oxygen were observed.