Sodium Bicarbonate → Ethyl 3-amino-4-hydroxybenzoate

Participants

Reaction Steps

In a 300 mL round bottom flask was placed, 3-amino-4-hydroxybezoic acid (5.50 g, 35.9 mmol), ethanol (200 mL), and a magnetic stir bar. The mixture was cooled in an ice bath to 10° C. and anhydrous HCl gas was bubbled through the stirred mixture until homogenous. The round bottom flask was then equipped with a condenser and the solution refluxed. After 1 hour the condensor was rearranged for distillation and 125 mL of ethanol was distilled off. The resulting solution was then dried in vacuo to give crude ethyl 3-amino-4-hydroxybezoate hydrochloride (7.73 g 35.5 mmol). Water (125 mL) containing NaHCO3 (3.0 g 35.7 mmol) was slowly added to the crude HCl salt and the resulting mixture was extracted 3×100 mL EtOAc. The EtOAc extracts were pooled, washed with brine, and then dried over NaSO4. The EtOAc was removed in vacuo to give ethyl 3-amino-4-hydroxybezoate (5.08 g, 78.0%) as a viscous oil which crystallized on standing. 1H NMR (600 MHz, CD2Cl2) δ 7.42 (d, J=2.0, 1H), 7.37 (dd, J=2.0, 8.2, 1H), 6.76 (d, J=8.2, 1H), 5.56-5.37 (s, 1H), 4.28 (q, J=7.1, 2H), 3.76 (s, 2H), 1.34 (t, J=7.1, 3H). 13C NMR (151 MHz, CD2Cl2) δ 167.79, 149.37, 134.83, 123.28, 122.37, 117.91, 114.98, 61.48, 14.63. MS (ES+) (m/z): [M+1]+ calculated for C9H12NO3, 182.08. found 182.09.

Provenance & Evidence