Primary Amine Syntheses from Olefins, Syngas and Ammonia

The selective preparation of aliphatic primary amines from an olefin, synthesis gas (CO/H₂), and ammonia has been developed involving the use of homogeneous catalysts comprising of cobalt octacarbonyl, phosphine ligand, and an ether or acetamide solvent system. 1-Hexene oxoamination typically yields a mix of C₇ plus C₁₄ primary amine in 57% selectivity. Process parameter studies involving changes in [NH₃], [Co], P/Co molar ratios, H₂/CO ratios, etc. provide some insight into the mechanism of this multi-step synthesis and the practical limits (ca. 65%) to primary amine selectivity and yield.