Studies of the Organic Reactions of Metal Carbonyl. IV. The Acceleration Effect of the Addition of Organic Compounds on the Reaction of Olefin Oxide with Cobalt Hydrocarbonyl and on the Hydroformylation of Olefin Oxide

Abstract

Abstract It has been observed that organic compounds with various kinds of functional groups have an accelerating effect on the reaction of olefin oxide with cobalt hydrocarbonyl and on the hydroformylation of olefin oxide. 1) The addition of a relatively small amount of ethyl alcohol promotes the carbonylation of propylene oxide with cobalt hydrocarbonyl until it is about 120 times faster than that of the standard run, carried out without alcohol. The amount of the alcohol necessary for this effect is about 2.0 mol./mol. HCo(CO)4. As the reaction products, only compounds with a β-hydroxy-n-butyryl structure (ester and aldehyde) have been obtained. 2) The compounds other than ethyl alcohol, such as n- and t-butyl alcohol, ethylene chlorohydrin, acetone, tetrahydrofuran, ether, acetal, benzaldehyde, ethyl acetate and acetonitrile, also have the same effect on this reaction. Among these compounds, ethyl and butyl alcohols have the largest effect. On the other hand, phenol has no effect. The accelerating effect is considered to be due to the basicity of these compounds. 3) The reactions of styrene oxide and epichlorohydrin with cobalt hydrocarbonyl are also promoted by the addition of ethyl alcohol.A relatively small amount of the alcohol accelerates selectively, the carbonylation of styrene oxide which is comparatively readily hydrogenated with cobalt hydrocarbonyl.2) For epichlorohydrin, the following relationship was observed to exist at an early stage of the reaction: rate of the gas absorption=k[epichlorohydrin] [ethyl alcohol]. 4) The hydroformylation of ethylene oxide seems to be selectively promoted by the addition of ethyl alcohol, which gives β-hydroxypropionaldehyde, in a low yield.