Hydrogen Peroxide → 5-Bromo-3-methylthiophene-2-carboxylic acid

Participants

Reaction Steps

A solution of 50.4 g of sodium phosphate, monobasic, (1.5 mol) in 600 mL of water, followed by 131 mL of a 35% hydrogen peroxide solution were added to a solution of 5-bromo-3-methyl-thiophene-2-carbaldehyde (300 g, 1.46 mol), example 1-a, in 1.5 L of acetonitrile. The resultant solution was cooled to 0° C. with an external ice bath, and a solution of 170 g of sodium perchlorite in 2 L of water was added dropwise over a 2 hour period. The reaction mixture was allowed to warm to room temperature, and stirred for 1.5 h. The reaction was quenched with the addition of 10 g of sodium sulfite, and stirred for 15 min. The mixture was acidified to ca. pH 3 with 1 N HCl solution, and cooled to 0° C. An off-white precipitate was collected on a medium glass filter funnel. The precipitate was washed twice with water and then dissolved in ethyl acetate. The aqueous acetonitrile solution was extracted once with ethyl acetate, and the organic fraction was combined with the pervious ethyl acetate solution. The combined organic fractions were dried over anhydrous magnesium sulfate and concentrated under hi-vacuum to produce 305 g of a tan solid. 1H NMR (CDCl3, 200 MHz): δ=6.91 (s, 1H), 2.52 (s, 3H); MS: (−) m/z 218.92, 220.94 (M−1, 79Br/81Br)

Provenance & Evidence