876. GRESHAM, W. F., BROOKS, R. E. AND BRUNER, W. M. (E. I. du Pont de Nemours & Co.). Methyl 4-Oxobutyrate. United States Patent 2,549,454, Apr. 17, 1951. Chem. Abs., vol. 45, 1951. p. 8551.

Patent Abstracts

Olefins with CO and H₂ give a mixture of aldehydes and ketones. If the reaction is carried out at pressures above 300 atm., high yields of aldehydes are obtained to the almost total exclusion of ketones. Reduced fused Co. catalysts (10 gm.). 75 cc. Et₃O, and 42.1 gm. MeCHLCH₂ heated 2 hr. at 108º-120º under 470-790 atm. in a Ag-lined shaker tube with a 1 : 2 mixture of CO and H₂ gave 69.9 gm. PrCHO. C₂H₄, 140, CO, 140: H₂, 20: and cyclohexane, 900 gm. were pumped for 1 hr. through a Ag-lined tube 20 in. long, containing 65 cc. metallic CO catalyst, at 140º under 700 atm., to give 90% EtCHO. Cyclohexane (82.1 gm.). 75 cc, Et₂O, and 10 gm. Co catalyst containing 3% Cu processed 2 hr. in a Cu-lined shaker tube under 580-790 atm. of CO:4H₂at 110º-112º gave 41.5 gm. hexahydrobenzaldehyde b_19-2055º-60º CH₂:CHCO₂Me (43 gm.). 0.5 gm. p-C₆H₄ (OH)₂, 100 cc. HCO₂Me, and 10 gm. Co catalyst processed 1 hr. in a shaker tube with CO:₂H₂ under 390-730 atm. at 145º-167º gave 57.4% Me4-oxobutyrate, b₁₀ 62º. H₂O (100 cc.). 10 gm. reduced 65% Co-35% Fe catalyst, and 28 gm. C₂H₄ heated 1.5 hr. at 110º-178º under 550-730 atm. of CO : 2H₂ in a stainless steel shaker tube gave 13.3 gm. EtCHO and 15 gm. EtCH : CMeCHO, b. 135º-139º.