Synthesis
General procedure for the synthesis of phenyl 3-(bromomethyl)acetate from 3-hydroxybenzyl alcohol: 3-hydroxybenzyl alcohol (37.2 g, 0.3 mol) was dissolved in 100 ml of pyridine, and acetic anhydride (81.7 g, 0.8 mol) was added slowly with stirring while the reaction temperature was raised to 70 °C. The reaction mixture was stirred at 70 °C for half an hour and then poured into a mixture of ice and hydrochloric acid. The organic phase was separated and the aqueous phase was extracted twice with dichloromethane. The organic phase and the dichloromethane extract were combined and washed sequentially with sodium bicarbonate solution, water, dilute acid and water. The organic phase was dried with anhydrous magnesium sulfate, filtered and the solvent was evaporated under reduced pressure to give 55.7 g of crude product (87% yield). The crude product was dissolved in 150 g of 30-32% hydrogen bromide in acetic acid solution and reacted for 10 min followed by addition of 25 ml of acetic anhydride. The mixture was allowed to stand overnight at room temperature. After completion of the reaction, it was evaporated under reduced pressure to an oil. The oily substance was dissolved in dichloromethane and washed sequentially with water, aqueous sodium bicarbonate solution and water. The organic phase was dried with anhydrous magnesium sulfate, filtered and the solvent evaporated under reduced pressure. The obtained oily substance was placed in a refrigerator for one week to allow slow crystallization.
References
[1] Tetrahedron, 2000, vol. 56, # 29, p. 5169 - 5175
[2] Patent: US4476207, 1984, A
