[Synthesis]
General procedure for the synthesis of 2-amino-4-(hydroxymethyl)phenol and o-amino-p-cresol from 4-hydroxy-3-nitrobenzaldehyde: A mixture of 0.30 g (1.8 mmol) of 4-hydroxy-3-nitrobenzaldehyde with 0.15 g of 10% Pd/C catalyst in 30 mL of ethanol was placed in a hydrogenation reactor and reacted with oscillation for 4 hours under hydrogen atmosphere at 30 psi. Upon completion of the reaction, the mixture was filtered through diatomaceous earth and carefully washed with ethyl acetate. After concentrating the filtrate, it was separated by silica gel column chromatography using a solvent mixture of dichloromethane and methanol (9:1) as eluent to give 91 mg (41% yield) of 2-amino-4-(hydroxymethyl)phenol and 0.10 g (41% yield) of o-amino-p-toluol.
Characterization data for compound 2-amino-4-(hydroxymethyl)phenol: IR (pure) ν 3370 (sharp, medium intensity), 3301 (sharp, medium intensity), 2921, 1601, 1519, 1458, 1388, 1286, 878, 800 cm^-1 ; ^1H NMR δ 6.62 (d, J = 7.6 Hz, 1H), 6.58 (d, J = 1.6 Hz, 1H), 6.48 (dd, J = 7.6, 1.6 Hz, 1H), 2.21 (s, 3H); ^13C NMR δ 141.9, 134.4, 131.2, 120.0, 118.1, 115.4, 20.9.
Characterization data for the compound o-amino-p-cresol: IR (pure) ν 3387 (sharp, medium intensity), 3313 (sharp, medium intensity), 3047 (broad), 2802, 1605, 1515, 1454, 1364, 1286, 1221, 1155, 1008, 816 cm^-1; ^1H NMR (D2O) δ 6.88 (d , J = 1.2 Hz, 1H), 6.85 (d, J = 8 Hz, 1H), 6.77 (dd, J = 8, 1.2 Hz, 1H), 4.49 (s, 2H); ^13C NMR (DMSO-d6) δ 142.9, 136.1, 133.5, 114.9, 113.8, 113.4, 63.3. |