5-Amino-1,3-dihydroxymethylbenzene

71176-55-1

71176-54-0

5-Nitro-m-xylene-α,α′-diol (1.07 g, 5.84 mmol) was used as the starting material, which was dissolved in methanol (50 mL) and Pd/C (10%, 311 mg, 0.29 mmol) was added as a catalyst. The hydrogenation reaction was carried out at 5 psi hydrogen pressure for 2 h at room temperature after hydrogen was introduced to displace the air in the reaction system. Upon completion of the reaction, the catalyst was removed by diatomaceous earth filtration and the filtrate was concentrated by rotary evaporation to afford 5-amino-m-xylene-α,α′-diol (26) as a white solid (900 mg, 100% yield).1H NMR (400 MHz, MeOD): δ 6.71 (s, 1H), 6.66 (s, 2H), 4.51 (s, 4H); 13C NMR (400 MHz, MeOD): δ 148.9, 143.8, 116.7, 114.3, 65.5. Compound 26 was dissolved in anhydrous acetonitrile (30 mL), and ethyl bromoacetate (443 μL, 4.67 mmol) and potassium carbonate (807 mg, 5.84 mmol) were added sequentially. The reaction mixture was refluxed at 86 °C in an oil bath for 17 hours. At the end of the reaction, it was cooled to room temperature, diluted with dichloromethane, filtered through diatomaceous earth and the solid was washed with dichloromethane. A white precipitate precipitated from the filtrate and was collected by filtration to afford 5-amino-1,3-dihydroxymethylbenzene (27) as a white solid (414 mg, 39% yield).1H NMR (400 MHz, MeOD): δ 6.67 (s, 1H), 6.53 (s, 2H), 4.51 (s, 4H), 3.94 (s, 2H), 3.73 (s, 3H ); 13C NMR (400 MHz, MeOD): δ 174.0, 149.7, 143.9, 116.2, 111.6, 65.6, 52.6, 46.5; MS (m/z): measured value 248.0 (M + Na)+.