Selective synthesis of N-aryl hydroxylamines by the hydrogenation of nitroaromatics using supported platinum catalysts

Abstract

Various substituted nitroaromatics were successfully hydrogenated to the corresponding N-aryl hydroxylamines in excellent yields (up to 99%) using supported platinum catalysts such as Pt/SiO₂ under a hydrogen atmosphere (1 bar) at room temperature. The key to the fast and highly selective formation of hydroxylamines is the addition of small amounts of amines such as triethylamine and dimethyl sulfoxide; amines promote the conversion of nitroaromatics, while dimethyl sulfoxide inhibits further hydrogenation of hydroxylamines to anilines. The promotive effect depends on which type of amine and primary amine was most effective. The hydrogenation efficiently proceeded in common organic solvents, including isopropanol, diethyl ether, and acetone. This methodology should extend the application range of conventional solid catalysts to fine chemicals synthesis.