867. ------. [GREESHAM, W. F., AND BROOKS, R. E.] (E. I. du Pont de Nemours & Co.). Reaction Between Olefinic Compounds, Carbon Monoxide, and Hydrogen in the Presence of a Metal Carbonyl Catalyst. United States Patent 2,497,303, Feb. 14. 1950: appl. f

Patent Abstracts

867. ------. [GREESHAM, W. F., AND BROOKS, R. E.] (E. I. du Pont de Nemours & Co.). Reaction Between Olefinic Compounds, Carbon Monoxide, and Hydrogen in the Presence of a Metal Carbonyl Catalyst. United States Patent 2,497,303, Feb. 14. 1950: appl. filed May 23. 1945: Serial No. 595,475: 3 claims (Cl. 260-604). Chem. Abs., vol. 44, 1950, p. 4492.

Outstanding results are obtained with Co, Ni, and Fe carbonyls. Amount of catalyst is preferably 0.1-10%, based on total weight of the reaction mixture, but Co carbonyl will exert an effect even when present to an extent of only 200 parts per 1,000,000 or less. In synthesis of O-containing compounds from ethylene, CO, and H₂ at pressures below 300 atm., the following 2 reactions occur: (1) CH₂=CH₂+CO+H₂→CH₂CH₂CHO: (2) 2 CH₂=CH₂+CO+H₂→CH₃CH₂COCH₂CH₂. According to the invention the effect of pressure above 375 atm. is to suppress (2), making possible the formation of aidehyde (1) in high yield. The pressure may be 3,000 atm. or higher. Molar ratio of CO : H₂ : olefin is 1 : 2 : 1-2 : 4 : 1. CO under high pressure is effective in suppressing thermal decomposition of thermally unstable carbonyls such as Co carbonyl. An inert liquid, such as xylene or diethyl benzene, may be used as reaction medium. When the catalyst is to be recovered by separating the aldehyde product at elevated temperature under high CO pressure, the boiling point of the medium should be above the boiling point of the principal aldehyde. Gives 14 examples. 2 literature refs., 1 foreign patent, and 3 United States patents cited.