Hydrochloric Acid → (2-Amino-3-chlorophenyl)amine

Participants

Reaction Steps

To a solution of 3-chloro-2-nitroaniline (10.00 g, 57.95 mmol), 3 N aq. HCl (96.58 mL, 289.7 mmol), and ethyl alcohol (148.6 mL, 57.95 mmol) was added Tin(II) chloride dihydrate (65.96 g, 289.7 mmol) and the mixture was heated under reflux with stirring. After 3 h, the mixture was cooled to room temperature and concentrated under reduced pressure to give a brown syrup. The mixture was cautiously treated with an excess of 10 M KOH (115.9 mL, 1159 mmol, 20 eqv.). The mixture was diluted with EtOAc (200 mL), filtered through Celite™ pad, and washed the pad well with EtOAc (100 mL×2). The filtrate was extracted with EtOAc (100 mL×2). The combined organic layers were washed with water (100 mL×1), dried over MgSO4, filtered, and concentrated under reduced pressure to give 3-chlorobenzene-1,2-diamine as a red oil: 1H NMR (400 MHz, DMSO-d6) δ ppm 6.43-6.53 (2 H, m), 6.38 (1 H, t, J=7.8 Hz), 4.80 (2 H, s), 4.60 (2 H, s); LCMS (ESI) m/z 142.9 [M+H]+. The crude product was carried on crude without purification for the next step.

Provenance & Evidence