Applications of Homogeneous Water-gas-shift Reaction. II. The Formation of Dipropyl Ketones as Primary Products from CO and H2O in the Presence of an Excess Amount of Propene. Cobalt-based Catalytic Hydrocarbonylation

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Abstract
The hydrocarbonylation of propene with CO and H2O to give dipropyl ketones occurs predominantly over forming C4-aldehydes; the catalyst solutions employed are prepared in situ from Co2(CO)8, various phosphines as ligands, and H2O, a high molar ratio of propene to Co2(CO)8 of 300/2 being required. Of the several phosphorus ligands examined, 1,2-bis(diphenylphosphino) ethane (diphos) and bis(diphenylphosphino) acetylene are relatively effective for the formation of the ketones (abbreviated as [ketones]). The effects of the reaction variables (CO pressure, temperature, and H2O concentration) on [ketones] are also examined using the Co2(CO)8–diphos system; [ketones] increases with the initial increase in CO pressure, but reaches a maximum at ca. 100 kg/ cm2 and decreases thereafter. Pronounced decreases of [ketones] are observed when pyridine as well as hydrogen is added to the catalyst solutions.