2-Cyanobenzyl bromide

529-19-1

22115-41-9

General procedure for the synthesis of 2-cyanobenzyl bromide from o-toluonitrile: Azobisisobutyronitrile (AIBN, 29.25 mmol) was added to a solution of 2-methylbenzyl cyanide (325 mmol) and N-bromosuccinimide (NBS, 346 mmol) in carbon tetrachloride (300 mL). The reaction mixture was heated at 90°C for 2 h and subsequently cooled to room temperature. The precipitated solid was removed by filtration and the filtrate was washed with saturated aqueous sodium bicarbonate solution (4 x 120 mL), dried over sodium sulfate and concentrated. The resulting solid was washed with hexane (4 x 500 mL) and dried to give 2-(bromomethyl)benzonitrile in 57% yield as a yellow solid. A solution of 2-(bromomethyl)benzyl cyanide (214 mmol) in dimethyl sulfoxide (40 mL) was slowly added to a solution of ethyl 2-hydroxyacetate (431 mmol) and sodium ethoxide (215 mmol) in dimethyl sulfoxide (14.5 mL) over 90 minutes. The reaction mixture was kept at room temperature for 1 hour, followed by heating at 65°C for 5 hours and finally cooled to room temperature. The reaction mixture was diluted with ice water (50 g), extracted with ether (3 x 500 mL) and the combined organic layers were dried over sodium sulfate and concentrated. The residue was purified by column chromatography (petroleum ether/ethyl acetate, 100:1 to 50:1) to give [(2-cyanobenzyl)oxy]ethyl acetate as a yellow oil.