Réaction #7184

Équation de réaction

3-nitroanisole

O-methylhydroxylamine hydrochloride

potassium tert-butoxide

→

2-amino-3-methoxy-nitrobenzene

Rendement 50.5%

Solvants

DMF

DMF

Conditions de réaction

Traitement

1. 1
   AutreThe cooling bath was removed
2. 2
   workup.ADDITIONThe reaction mixture was poured into saturated aqueous NH4Cl (50 mL)
3. 3
   Extractionthe mixture was extracted with CH2Cl2 (4×50 mL)
4. 4
   SéchageThe combined organic extracts were dried (Na2SO4)
5. 5
   Concentrationconcentrated
6. 6
   AutrePurification of the crude material by column chromatography on silica gel (5:1 hexanes-ethyl acetate)

Mode opératoire

A suspension of 3-nitroanisole (1.550 g, 10.12 mmol) and O-methylhydroxylamine hydrochloride (1.078 g, 12.91 mmol) in DMF (15 mL) was added to a cold (0° C.) solution of potassium tert-butoxide (5.870 g, 52.30 mmol) and copper(I) chloride (0.200 g, 2.02 mmol) in DMF (35 mL). The cooling bath was removed and the resultant slurry was stirred at room temperature for 6 hours. The reaction mixture was poured into saturated aqueous NH4Cl (50 mL) and the mixture was extracted with CH2Cl2 (4×50 mL). The combined organic extracts were dried (Na2SO4) and concentrated. Purification of the crude material by column chromatography on silica gel (5:1 hexanes-ethyl acetate) followed by radial chromatography on silica gel (2 mm plate, 5:1 hexanes-ethyl acetate) provided 0.860 g (50%) of 2-amino-3-methoxy-nitrobenzene as a red solid. 1H NMR (CDCl3) □ 3.92 (s, 3H), 6.44 (br s, 2H), 6.61 (dd, 1H, J=9.0, 9.0 Hz), 6.88 (d, 1H, J=9.0 Hz), 7.74 (d, 1H, J=9.0 Hz).

Source