Switchable synthesis of furfurylamine and tetrahydrofurfurylamine from furfuryl alcohol over RANEY® nickel

RANEY® Ni proved to be an effective heterogeneous catalyst for switchable reductive amination of furfuryl alcohol to tetrahydrofurfurylamine and furfurylamine with NH 3 by simply adding or not adding 1.0 MPa H 2 into the reaction bulk. After further optimization of the reaction conditions, we finally obtained 94.0% yield of tetrahydrofurfurylamine and 78.8% yield of furfurylamine with high selectivity. By extensively studying the catalytic pathways and mechanism of catalyst deactivation with XRD and XPS characterization, we have confirmed that an excess amount of H 2 in the reaction bulk leads to the deep hydrogenation of the furan ring while an insufficient amount of H 2 leads to the formation of Ni 3 N and the deactivation of the catalyst.