4-Bromo-5-(chloromethyl)-2-methoxyphenol

2-Bromo-5-hydroxy-4-methoxybenzenemethanol [1] (38.8 g, 166 mmol) in dry chloroform (200 mL) was treated with thionyl chloride (200 mL, 2.76 mol) at 0 °C and stirred for 3 h at ambient temperature. The solvent was removed in vacuo, the residue was dissolved in Et₂O and washed with water (3 x 100 mL), satd. NaHCO₃ (4 x 150 mL) and brine (200 mL), dried over Na₂SO₄, filtered and concentrated in vacuo. The residue was triturated with iPr₂O (2 x 50 mL). Yield: colorless crystals (38.8 g, 93%), mp. 112 - 115 °C.

TLC: petroleum ether : EtOAc = 90 : 10, R_f = 0.5.

Anal. Calcd for C₈H₈BrClO₂: C, 38.21; H, 3.21. Found: C, 38.46; H, 3.14.

¹H NMR (CDCl₃). δ 7.05 (s, 1H), 7.00 (s, 1H), 5.65 (s, 1H), 4.60 (s, 2H), 3.85 (s, 3H).

¹³C NMR (CDCl₃). δ 147.3 (s), 145.2 (s), 129.4 (s), 116.6 (s), 115.1 (d), 113.4 (d), 56.3 (t), 46.2 (q).