Ethyl 2-(bromomethyl)-4-methoxybenzoate synthesis

Yield:56427-63-5 52%

Reaction Conditions:

with N-Bromosuccinimide;dibenzoyl peroxide in tetrachloromethane at 78;

Steps:

25.B

Step B: Synthesis of ethyl 2-(bromomethyl)-4-methoxybenzoate as an intermediate ; [0175] A mixture of ethyl 4-methoxy-2-methylbenzoate (2.24 g, 11.5 mmol) in carbon tetrachloride (20 mL) was heated to 78 ⁰C in an oil bath then a mixture of N- bromosuccinimide (2.26 g, 12.6 mmol) and benzoyl peroxide (0.28 g, 1.15 mmol) was added portionwise over 4 h. The mixture was stirred overnight at 78 °C. After this time, the reaction mixture was cooled to room temperature and the solids removed by filtration. The filtrate was concentrated under reduced pressure and purification by flash chromatography (silica, 1 :50 ethyl acetate/hexanes) afforded ethyl 2-(bromomethyl)-4-methoxybenzoate (1.60 g, 52%) as a clear oil: ¹H NMR (300 MHz, CDCl₃) δ 7.99 (d, J= 8.7 Hz, IH), 6.96 (s, IH), 6.86 (dd, J= 8.7, 2.6, IH), 4.96 (s, 2H), 4.37 (q, J= 7.1, 2H), 3.86 (s, 3H), 1.41 (t, J= 7.1 Hz, 3H); ESI MS m/z 273 [M+ H]⁺.

References:

WO2009/42907,2009,A1 Location in patent:Page/Page column 69-70