2,6-Dinitrotoluene → 3-Methyl-2,4-dinitroaniline

Participants

Reaction Steps

2,4-dinitro-3-methylaniline was prepared by a modification of the procedure described by Meisenheimer, et al., Chem. Ber. (1906) 39:2533. A mixture of 2,6-dinitrotoluene (55.0 g) and hydroxylamine hydrochloride (55.0 g) was stirred in 1.4 L of ethanol until solution took place. 2N Potassium hydroxide solution (550 mL) was added all at once and the resulting mixture allowed to stir for 24 hr. A solution of ammonium chloride (71 g) in water (350 mL) was added and the mixture stirred for an additional hour. The reaction mixture was evaporated under reduced pressure. The residue was partioned between ethyl acetate (750 mL) and 50% saturated sodium chloride solution (500 mL). The ethyl acetate extract was separated and dried over magnesium sulfate. Evaporation under reduced pressure afforded a crude product (52.6 g) which was flash chromatographed on silica and eluted, first with ethyl acetate:hexane (1:3), then with ethyl acetate:hexane (1:2) to afford 36.0 g of product, mp 126.7-131.4° C.

Provenance & Evidence