LAUSR

A new approach to resolve the problem of selectivity with respect to N-phenylhydroxylamine in nitrobenzene hydrogenation is proposed. N-phenylhydroxylamine only is the final product of nitrobenzene electroreduction in aprotic media. In this case nitrobenzene reduction carries out by alternation of electrochemical (electron transfer) and chemical (species formed protonation) stages i.e. by so-called EC mechanism. Such mechanism realization in nitrobenzene hydrogenation is possible if i) a catalyst activates hydrogen as “hydrogen electrode” i.e. serves electrons source; ii) a reaction media contains limiting proton concentration. These limitations are discharged in the media of aprotic dipolar solvent, which solvated both positive and negative species. Really, in aprotic dipolar solvents over reduced platinum complexes or lowpercentage (≤1 wt.%) platinum, iridium or osmium catalyst nitrobenzene is hydrogenated with process discontinuance after nitrobenzene total consumption. Nitrobenzene hydrogenation yields N-phenylhydroxylamine as the main (the yield is 98%) product. As these low-percentage catalysts, complex catalyst in situ is heterogeneous i.e. it represents a platinum colloid (particle size ~ 40 nm) stabilized by aprotic dipolar solvent. So, process of nitrobenzene  hydrogenation, which is similar to nitrobenzene electoreduction, can is created. A kinetic scheme proposed is analyzed and kinetic equation for initial reaction rate, which is conformed to kinetic data, is obtained.