1965 Volume 38 Issue 10 Pages 1649-1654
The reaction of olefin oxide with cobalt hydrocarbonyl in the presence of inorganic (and organic) additives has been investigated.
1) The addition of relatively small amounts of various compounds of copper and silver promote the carbonylation of propylene oxide. The order of the promoting effect of these compounds is Cu2O, 70>CuO, 6O>(AlCl3, 30) >Ag2O, 27>CuCl2, CuCl and Cul, 20>CuCN, 15>AgCl, 9>Cu powder, 4>None, 1 (the numbers indicating the relative rates of the gas absorption at the early stage of the reaction). Among these, cuprous oxide has the largest effect. The amount of cuprous oxide necessary for this effect is only about 0.005 mol./mol. HCo(CO)4. β-Hydroxy-/n-butyrate has been the main reaction product obtained. On the other hand, chlorides of zinc, nickel, ferric, potassium, magnesium, palladium and titanium have no promoting effect on the reaction.
2) The combination of cuprous halide (and oxide) with various organic additives, which also have a promoting effect, has a synergistic effect on the reaction of propylene oxide.
3) The reaction of epichlorohydrin is also promoted by the addition of cuprous oxide. However, in this case cuprous oxide combined with ethyl alcohol has a retardation effect.
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