Selective Synthesis of Primary Amines from Nitriles under Hydrogenation Conditions

The hydrogenation of aliphatic nitriles over Pd/C, Pd/Al2O3, and Pd−Au/Al2O3 catalysts were evaluated for the selective hydrogenation of aliphatic nitriles to the corresponding primary amines. The highest selectivity (>99%) toward primary amines was achieved when the reaction was carried out in acetic acid using 10 mol% of 25% Pd‐5% Au/Al2O3 under relatively low hydrogen pressure (0.8 MPa). Characterization of the catalysts by XRD, CO adsorption experiments, and EXAFS revealed that the excellent selectivity of 25% Pd‐5% Au/Al2O3 toward the synthesis of primary amines is determined by the electronic properties and/or the surface structure resulting from alloying Pd with Au.