2104. LEVESQUE, C. L. Oxo Reactions in Industry. Chem. Eng. News, vol. 28, 1950, No. 45, p. 3881. Paper presented at the October meeting of the Philadelphia and Wilmington Organic Chemists Clubs. The industrial use of certain Oxo reactions and their mechanism were discussed. Certain rules for the addition of CO and H2 to unsubstituted olefins were presented: (1) Isomerization of the double bond, if possible, generally accompanies the hydroformylation; (2) straight-chain olefins give 40-60% straight-chain aldehydes, and 60-40% of other isomers, the a-methyl one predominating; (3) addition of an aldehyde group to a tertiary C does not occur, no quaternary C atom is found; (4) addition of an aldehyde group adjacent to a tertiary C atom is strongly hindered, but may occur to a small extent; (5) the tertiary C atom does not hinder seriously if the double bond is in the 1, 2-position; (6) addition of the aldehyde group adjacent to a quarternary C does not occur. Several examples are given of reactions that have been run, together with products and yields obtained. The mechanism of the Oxo reduction is believed to center around Co carbonyl or Co carbonium hydride as the actual catalyst. The reaction mechanism must explain the fact that the formyl group always goes on the least substituted C atom, and, except in the case of styrene, the formyl group always appears on the β carbon of an a, β-unsaturated compound. |