Cataytic Hydrogenation of o-Nitrochlorbenzene to 3,3'-Dichlorobenzidine

2,2'-Dichlorohydroazobenzene was prepared by selective hydrogenation of o-nitrochlorobenzene with hydrogen in the presence of 0.8% and 5% Pd/C catalyst. O-Chloroaniline was a minor product in the catalytic hydrogenation of o-nitrochlorobenzene. The effects of base, Pd/C catalyst, and co-catalyst were discussed on catalytic hydrogenation. 2,2'-Dichlorohydroazobenzene, as an intermediate, was rearranged to 3,3'-dichlorobenzidine after reacting with HCl. It was shown that selectivity of catalytic hydrogenation of o-nitro-chlorobenzene is affected strongly by concentration of base, Pd/C catalyst, and co-catalyst. $^1Hand^{13}C$NMR spectroscopy confirmed the chemical structures of 2,2'-dichlorohydrazobenzene and 3,3'-dichlorobenzidine.