LIGAND EFFECTS IN THE HYDROFORMYLATION OF ACRYLONITRILE BY COBALT CARBONYL

Article abstract of DOI:10.1016/0022-328X(83)80026-6

The hydroformylation of acrylonitrile (VCN) using Co2(CO)8/L (L = HN(CH2CN)2, , Me2N(CH2)2NMeH, PPh3, and PCy3) has been examined in methanol solvent.Four reaction pathways are observed which are dependent on L.With no L or with L = HN(CH2CN)2, the reaction produces the desired acetal (MeO)2CHCH2CH2CN.For the more basic amines the reactin produces ca. 50percent yields of hydrodimerization products NCCHMe(CH2)2CN/NC(CH2)4CN in a 10/1 ratio and an ca. 30percent yield of the hydrogenation product CH3CH2CN.These reactions are shown to be metal catalyzed.The main reactionfor Co2(CO)8/PR3 catalyzed systems appears to be a classical Michael addition reaction of the solvent, methanol, with acrylonitrile to give MeOCH2CH2CN.Evidence is given to show that this reaction is catalyzed by phosphine which has dissociated under reaction conditions and not by a ligated cobalt complex.