Nitric Acid → 3-Chloro-6-nitrotoluene

Concentrated nitric acid (16 mL) was slowly added, at 0° C., to a solution of 3-chlorotoluene (3 mL, 25.4 mmol) and concentrated sulfuric acid (6 mL) in glacial acetic acid (20 mL) and the resulting mixture was stirred for 24 hours allowing the temperature to rise until room temperature. The reaction mixture was then poured into ice-water and partitioned between water and diethyl ether. The aqueous phase was separated and extracted twice with diethyl ether; the combined organic extracts were washed with water and brine, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The yellow oily residue was purified on a silica gel plug and twice by flash chromatography to give 1.22 g (14% yield) of 2-chloro-4-methyl-1-nitro-benzene as a yellow oil and 3.39 g (39% yield) of 4-chloro-2-methyl-1-nitro-benzene.