5-Chloro-2-nitrotoluene

108-41-8

5367-28-2

38939-88-7

General procedure for the synthesis of 5-chloro-2-nitrotoluene and 3-chloro-4-nitrotoluene from 3-chlorotoluene: Concentrated nitric acid (16 mL) was added slowly and dropwise at 0°C to a solution of glacial acetic acid (20 mL) containing 3-chlorotoluene (3 mL, 25.4 mmol) and concentrated sulfuric acid (6 mL). The reaction mixture was stirred at room temperature for 24 hours. Subsequently, the reaction mixture was poured into ice water and liquid-liquid partitioned with ether. After separating the aqueous phase, the aqueous phase was extracted twice with ether. The organic phases were combined, washed sequentially with water and brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The yellow oily crude product obtained was purified by silica gel column chromatography and after two rapid chromatographic separations, 1.22 g (14% yield) of 5-chloro-2-nitrotoluene (yellow oily) and 3.39 g (39% yield) of 3-chloro-4-nitrotoluene were obtained.