Benzoyl Peroxide → Methyl 4-bromo-2-(bromomethyl)benzoate

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Reaction Steps

Treat a solution of 15.0 gm. (0.0655 mole) of methyl 5-bromo-o-toluate in 75 ml. of carbon tetrachloride portionwise during 30 minutes with a mixture of 12.83 gm. (0.0721 mole) of N-bromosuccinimide and 130 mg. of benzoyl peroxide. Heat the resulting mixture under reflux for 3 hours. Cool to room temperature and separate the succinimide by filtration. Remove the solvent under vacuum to obtain methyl α,5-dibromo-o-toluate as a yellow residual oil. Heat a mixture of 9.05 gm. (0.0655 mole) of 3,4-methylenedioxyphenol, 75 ml. of dimethylformamide, 27.16 gm. (0.1965 mole) of potassium carbonate and the methyl α,5-dibromo-o-toluate obtained above at 55°-60° C. for 2 hours. Cool the mixture and pour into 350 ml. of water. Extract the resulting oil into ether, wash with water and dry over anhydrous magnesium sulfate. Remove the solvent under vacuum to obtain the title product as a waxy solid (yield 23.92 gm.). Recrystallize from cyclohexane to obtain pure product as yellow needles [yield 16.12 gm. m.p. 93°-98° C., pmr (CDCl3) 3.88 (3H,s, CH3O--), 5.30 (2H,s,CH2O--), 5.85 (2H, s,OCH2O--)].

Provenance & Evidence