3652. WENDER, I., LEVIN, R., AND ORCHIN, M. Chemistry of the Oxo and Related Reactions. I. Homologation of Alcohols. Jour. Am. Chem. Soc., vol. 71, 1949, pp. 4160-4161; Chem. Abs., vol. 44, 1950, p. 2439.
Investigations at the Bureau of Mines have revealed that an alcohol can be converted to the homologous alcohol containing 1 C atom more than the original one by the Oxo or hydroformylation reaction without proceeding via an olefin intermediate followed by a 1-step hydroformylation-hydrogenation. The process is to treat the alcohol with synthesis gas, 1H2:1CO, at 160°-180° and 3,200 p.s.i. for 1-1.5 hr. in the presence of a Co catalyst, cobaltous acetate, or cobaltous oxide. By this means, benzyl alcohol is converted to β-phenylethyl alcohol, isopropyl alcohol to n-butyl and isobutyl alcohol, and t-butyl alcohol to isoamyl alcohol. It is believed that the homologation reaction is an acid, HCoCO4, catalyzed reaction that proceeds via a carbonium ion according to a mechanism that will be discussed later.