3-BROMO-4-METHYLPHENOL

off-white crystalline

(1 eq ., 5 g, 26.7 mmol) was dissolved in DCM (200 ml_) along with triethylbenzylammonium chloride (5 %, 0.304 g, 1.34 mmol) and dimethyl sulfate (1.2 eq., 4.05 g, 3.04 ml_, 32.1 mmol). Then, under vigorous stirring, NaOH (19 M, 2.5 eq ., 3.5 ml_) was added dopwise at room temperature. The reaction mixture became orange and turbid, then after 2 hours it regained its original greenish color. Water was then added (100 ml_), and the mixture was stirred for 1 more hour. Then an ammonium hydroxide solution (10 ml_) was added to quench the excess dimethyl sulfate, and the mixture was stirred for 1 more hour. The phases were then separated and the organic phase was washed with a 1 M NaOH solution (1 M), a sat. sol . of NaHC03, and with a 1 M HCI solution (2 times). The product 2-bromo-4-methoxy-l-methylbenzene (5.02 g, 25 mmol, 93 %), isolated as an orange oil, is pure enough to be used in the next step (the crude given in the SI).1H-NMR (CDCIs, 400 MHz) : d = 7.12 (d, J = 8.4 Hz, 1H), 7.10 (d, J = 2.6 Hz, 1H), 6.77 (dd, J = 8.4, 2.7 Hz, 1H), 3.77 (s, 3H), 2.33 (s, 3H) ppm.Spectral data matched the literature.