A study on the selective hydrogenation of nitroaromatics to N-arylhydroxylamines using a supported Pt nanoparticle catalyst

A supported Pt nanoparticle-based catalyst was used in the chemoselective hydrogenation of nitroarenes to N -arylhydroxylamines ( N -AHA). Optimization of NB hydrogenation conditions showed that substantially higher N -PHA yields can be obtained at low temperature. Especially, the influence of an increased hydrogen pressure on selectivity is remarkable. Maximum yields increase from 55% N -PHA at 4 bar H 2 to 80% at 23 bar H 2 in ethanol. Further optimization led to the use of small amounts of amine additive, TMEDA, with 50 bar H 2 raising the maximum yield to 97% N -PHA. The decreased N -PHA hydrogenation rate at high H 2 pressure and the presence of TMEDA allow for selective transformation of a range of other nitroarenes containing electron-withdrawing and -donating (reducible) functional groups to their N -AHAs in excellent (more than 90%) yields.