4-Methyl-2-nitroaniline → 2-Bromo-4-methyl-6-nitroaniline

Participants

Reaction Steps

A solution of bromine (23.24 mL, 453.5 mmol) in glacial acetic acid (50 mL) was added dropwise over 2 h to a mechanically-stirred suspension of 4-methyl-2-nitroaniline (60.00 g, 394.3 mmol) in glacial acetic acid (200 mL) at room temperature under a nitrogen atmosphere. The mixture was stirred at room temperature 1 h, and then most of the acetic acid was removed under reduced pressure. The resultant orange solid was dissolved in a mixture of saturated aqueous sodium bicarbonate (1500 mL) and ethyl acetate (500 mL). The layers were separated and the aqueous solution was again extracted with ethyl acetate. The combined organic layers were washed once with water, dried (MgSO4), filtered, and concentrated under reduced pressure to afford the title compound of Step A as an orange solid melting at 64°-65.5° C. (89.694 g, 98%). 1H NMR (CDCl3): δ2.28 (s,3H), 6.45 (br s,2H), 7.55 (s, 1H), 7.94 (s, 1H).

Provenance & Evidence