Methanol → 4-(Allylamino)benzoic acid

Participants

Reaction Conditions

Reaction Steps

A 500 mL round-bottom flask, equipped with a magnetic stir bar and condenser was charged with compound 2 (2 g, 10.4 mmol), LiOH.H2O (1.18 g, 15.7 mmol), 100 mL MeOH and 60 mL H2O. The mixture was heated at 55° C. for 24 hours. The solution was concentrated in vacuo to remove methanol and most of H2O. Ehther/H2O=100 mL/100 mL was used to remove most of the unreacted starting material. The aqueous layer was acidified to pH 4.0 with 1M HCl and some white precipitation was formed. The product was extracted with ethyl acetate (3×70 mL). The combined organic layer was washed with brine and dried over NaSO4. After removal of the solvent, the crude product was purified by silica gel chromatography (eluent: Hexane/Ethyl acetate from 100:5 to 100:25). Recrystallization from ethyl acetate/hexane twice yielded white crystal (0.85 g, 46.1% yield). 1H NMR (400 MHz, CDCl3): δ 3.82 (d, 2H), 5.10 (dd, 1H), 5.23 (dd, 1H), 5.80-5.96 (m, 1H), 6.62 (d, 2H), 7.78 (d, 2H); 13C NMR (400 MHz, CDCl3): δ 46.07, 112.19, 116.06, 118.44, 132.30, 136.14, 153.63, 168.01; ESI-MS: Calcd for C10H12NO2 [M+1] 178.1, found 178.0; Anal. Calcd for C10H11NO2: C, 67.78; H, 6.26; N, 7.90. Found: C, 67.81; H, 6.28; N, 7.86. MP: 144-146° C.

Provenance & Evidence