Hydrochloric Acid → 1-Chloro-2-fluoro-4-methyl-5-nitrobenzene

Participants

Reaction Conditions

Reaction Steps

A solution of sodium nitrite (7.6 g, 110 mmol) in water (20 mL) was added dropwise over 30 min at 0° C. to a stirred suspension of 2-fluoro-4-methyl-5-nitroaniline (17 g, 100 mmol) in concentrated hydrochloric acid (200 mL). The mixture was stirred at 0° C. for 20 min then transferred to a dropping funnel and added dropwise over 30 min to a stirred suspension of copper(I)chloride (16 g) in concentrated hydrochloric acid (150 mL) at 0° C. The mixture was allowed to warm to room temperature and stirred for 16 h then poured onto ice-water (1.5 L) and extracted with ethyl acetate (3×). The combined organic extracts were washed with brine, dried (magnesium sulfate), concentrated in vacuo and purified by column chromatography [SiO2; heptane] to give the product (14.2 g, 75%) as a yellow solid. An analytical sample was recrystallised (heptane) to give a white solid: mp 57-58° C.; NMR δH (400 MHz, CDCl3) 8.03 (1H, d, J 7.2 Hz), 7.13 (1H, d, J 9.1 Hz), 2.6 (3H, s).

Provenance & Evidence