Methanesulfonic Acid → 3-(1-Adamantyl)-4-bromo-5-methoxyphenol

Participants

Reaction Conditions

Reaction Steps

A mixture of 4-bromo-3-methoxyphenol (6.33 g, 31.18 mmol), 1-adamantanol (4.75 g, 31.18 mmol) and MeSO3H (1.3 mL) in CH2Cl2 (22 mL) was stirred with heating at 54° C. (oil-bath) for 29 h. The resulting solution was quenched with H2O (30 mL) and extracted with EtOAc (140 mL). The extract was washed with H2O, 5% NaHCO3, and brine and dried. The residue obtained on concentration was purified on silica gel (0% to 15% EtOAc/hexane) to give 5.77 g (55%) of 3-(1-adamantyl)-4-bromo-5-methoxyphenol as a white solid, mp 151-153° C. and 2.71 g (26%) of 2-(1-adamantyl)-4-bromo-5-methoxyphenol as a white solid, mp 182-185° C. 3-(1-Adamantyl)-4-bromo-5-methoxyphenol: IR 3515, 2902, 2848, 1312, 1216 cm−1; 1H NMR δ (CDCl3) 1.75 (bs, 6H, AdCH2), 2.04 (bs, 9H, AdCH and AdCH2), 3.79 (s, 311, OCH3), 5.29 (s, 1H, OH), 6.57 (s, 1H, 6-ArH), 7.19 ppm (s, 1H, 2-ArH). 2-(1-Adamantyl)-4-bromo-5-methoxyphenol: IR 3513, 2902, 2848, 1389, 1207 cm−1; 1H NMR δ (CDCl3) 1.77 (bs, 6H, AdCH2), 2.06 (bs, 9H, AdCH and AdCH2), 3.83 (s, 3H, OCH3), 4.83 (s, 1H, OH), 6.29 (s, 1H, 6-ArH), 7.31 ppm (s, 1H, 3-ArH).

Provenance & Evidence