Amine synthesis via carbonylation reactions: aminomethylation

The preparation of aliphatic amines and alicyclic diamines by reaction of olefins, synthesis gas and dimethylamine, known as aminomethylation, was investigated. Synthesis involves homogeneous rhodium and ruthenium catalysts or mixtures thereof at very low concentrations. Employing 3–12 ppm Rh and 50–100 ppm Ru results in up to 97% selectivity towards the amines at conversions of up to 98% if aliphatic mono-olefins are used as starting materials. At high catalyst concentrations (173 ppm Rh, 2660 ppm Ru) the corresponding diamine is obtained from dicyclopentadiene in 89% yield. The influence of reaction parameters and catalyst ratios on the n/i-selectivity of the product indicates the scope as well as the limits of such a multi-step synthesis for a commercial process.