4-Amino-3-methyl-5-nitrobenzonitrile → 3,4-Diamino-5-methylbenzonitrile

Participants

Reaction Steps

To a solution of 4-amino-3-methyl-5-nitro-benzonitrile (3.24 g, 18.3 mmol) in ethanol (80 mL) was added tin chloride dihydrate (8.67 g, 49.75 mmol). The reaction mixture was heated to reflux for 14 h, then cooled to room temperature, and concentrated in vacuum. The residue was diluted with ethyl acetate (100 mL) and treated with triethylamine (20 mL). The resulting slurry was filtered through a pad of celite and the filtercake was rinsed with three-portion ethyl acetate (50 mL). The filtrate was washed with saturated NaHCO3, water, and brine, then dried over Na2SO4 and filtered. After removal of solvent, the residue was purified by flash chromatography on silica gel (30%–50% EtOAc/hexane) to yield the title compound (2.17 g, 81%) as a light yellow solid. 1H NMR (300 MHz, CDCl3) δ 6.94 (1H, s), 6.85 (1H, s), 2.16 (3H, s). LCMS (M+H)+ m/z 148 (t=0.67 min.).

Provenance & Evidence