3-Chloroperoxybenzoic Acid (contains ca. 30% Water)

• p-Anisidine [A0487]
• 3-Chloroperoxybenzoic Acid (contains ca. 30% Water) (= mCPBA) [C0357]
• 1,2-Dichloroethane

To a solution of p-anisidine (123 mg, 1.0 mmol) in 1,2-dichloroethane (7.5 mL) was added mCPBA (1.06 g, 4.0 mmol) at r.t. and the mixture was stirred at 90 °C for overnight. The reaction mixture was diluted with dichloromethane (25 mL) and washed with saturated aqueous sodium thiosulfate solution (50 mL) and saturated aqueous sodium bicarbonate solution (50 mL), dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the residue was purified by column chromatography (on silica gel, dichloromethane:hexane = 0:1 - 1:4), giving p-nitroanisole as a pale yellow solid (116 mg, 76%).

The reaction mixture was monitored by UPLC.

p-Nitroanisole

¹H NMR (270 MHz, CDCl₃); δ 8.21 (d, 2H, J = 9.2 Hz), 6.96 (d, 2H, J = 9.2 Hz), 3.91 (s, 3H).

• Oxidation of aromatic amines into nitroarenes with m-CPBA
• J. Liu, J. Li, J. Ren, B.-B. Zeng, Tetrahedron Lett. 2014, 55, 1581.

• 3-Chloroperoxybenzoic Acid (contains ca. 30% Water) (= MCPBA) [C0357]
• Dichloromethane

To a solution of compound 1 (0.20 g, 0.67 mmol) in dichloromethane (3.0 mL) was added MCPBA (0.42 g, 1.7 mmol) at 0 °C and stirred at ambient temperature for 40 hours. The solution was added sodium hydroxide (1.0 g, 25 mmol) in water (10 mL). The mixture was extracted with ethyl acetate (10 mL x 3), and organic phase was dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the residue was purified by column chromatography (ethyl acetate:hexane = 1:19 on silica gel) to give compound 2 (0.18 g, 82%) as a white solid.

The reaction mixture was monitored by UPLC.

Compound 2

¹H NMR (270 MHz, CDCl₃); δ 7.74-7.54 (m, 5H), 7.38-7.16 (m, 5H), 3.75-3.66 (m, 2H), 2.84 (t, J = 7.3 Hz, 2H), 2.38-2.24 (m, 2H).

• One-Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride
• J. Y. Mo, M. Epifanov, J. W. Hodgson, R. Dubois, G. M. Sammis, Chem. Eur. J. 2020, 26, 4958.