Hydrochloric Acid → 3-Bromo-5-methylaniline

Participants

Reaction Steps

In 2 L flask outfitted with condenser and stir bar was added 1-bromo-3-methyl-5-nitrobenzene (50.0 g, 231 mmol), ethanol (967 mL), and saturated aqueous NH4Cl (141 mL). The system was evacuated and flushed with N2(g) and then iron (38.8 g, 694 mmol) was added before heating the reaction to reflux for 2 days. The reaction was cooled to room temperature and CELITE (15 g) was added to the flask. This was then filtered through CELITE, washing the cake with ethanol (500 mL) and ethyl acetate (500 mL). The filtrate was concentrated and the solvent was removed. The residue was diluted with ethyl acetate (500 mL) and water (500 mL). After cutting the layers, the organic was washed with saturated aqueous NaHCO3 (400 mL) and then brine (400 mL), before drying over sodium sulfate and concentrating. MTBE (˜500 mL) was added to the resultant residue and HCl in dioxane (4 M, 57.9 mL, 231 mmol) was added dropwise at RT over 30 min. The resultant precipitate was collected by filtration. This creme colored solid was placed in a beaker and was dissolved in ethyl acetate and partitioned with saturated aqueous NaHCO3 and then 10% NH4OH (aq). The organic was cut and dried over sodium sulfate before concentrating to dryness. 3-Bromo-5-methylaniline was isolated as a brown oil. MS APCI calc'd for C7H9BrN [M+H]+ 186. found 186/188.

Provenance & Evidence