4-Bromo-2,6-difluorophenol (49)

To a solution of 2,6-difluorophenol (1.30 g, 10.0 mmol, 1.00 equiv) in anhydrous DMF at 0 °C under N₂, recrystallized NBS (1.87 g, 10.5 mmol, 1.05 equiv) was added in one portion, and the clear solution was stirred in the dark for 40 h while warming to r.t.. The reaction was quenched with H₂O, then extracted with Et₂O (×4). The combined organic extracts were washed with 1 M Na₂SO₃, brine, dried over MgSO₄, filtered, and concentrated in vacuo. Purification by silica gel column chromatography (10% EtOAc in hexanes) provided the title compound (1.80 g, 8.63 mmol, 86%) as a yellow solid: ¹H NMR (500 MHz, CDCl₃) δ 7.12–7.06 (m, 2H), 5.17 (s, 1H) ppm; ¹³C NMR (125 MHz, CDCl₃) δ 151.8 (dd, J = 246.8, 6.3 Hz), 132.6 (t, J = 15.8 Hz), 115.8–115.5 (m), 110.4 (t, J = 10.9 Hz) ppm; IR (KBr) ν 3214, 2974, 1812, 1644 cm^–1; HRMS (ES^–) calculated for C₆H₂BrF₂O [M–H]⁻ 206.9257, found 206.9250.