Hydrogenation of nitroaromatics by polymer-anchored bimetallic palladium-ruthenium and palladium-platinum catalysts under mild conditions

Polymer-anchored monometallic palladium catalyst PVP-PdCl2 (PVP = poly(N-vinyl-2-pyrrolidone)) exhibits very high activity for the hydrogenation of p-chloronitrobenzene (CNB) to aniline (AN) in the presence of base at 65 degrees C and atmospheric pressure. In this case, the substrate is rapidly hydrodechlorinated to nitrobenzene (NB) which is then reduced to AN. Using the polymer-anchored bimetallic palladium-ruthenium catalyst, PVP-PdCl2-RuCl3, and in the presence of 1.0 mol% of sodium acetate, a strong synergic effect gives rise to a remarkable increase of the selectivity for p-chloroaniline (CAN) and the maximum selectivity of CAN is up to 94%. For the hydrogenation of the non-halo-substituted nitroaromatics to the corresponding aromatic amines, the monometallic PVP-PdCl2 catalyst only shows mild or poor activity, but the colloidal polymer-anchored bimetallic palladium-platinum catalyst, PVP-Pd-1/4Pt, exhibits very high activity and selectivity.