Hydrogen Peroxide → Methyl 3-chloro-2-nitrobenzoate

Participants

Reaction Conditions

Reaction Steps

A solution of 5.3 g (16.2 mmol) of sodium tungstate dihydrate and 3.2 g (32.3 mmol) of concentrated sulfuric acid in 53 ml of methanol was heated to 40° C., and a solution of 15 g (80.8 mmol) of methyl 2-amino-3-chlorobenzoate in 13 ml of methanol, and 33.0 ml (323 mmol) of a 30% hydrogen peroxide solution were simultaneously added dropwise over 10 hours. The pH value at this time was 0.5. After the completion of the dropwise addition, the mixture was stirred at 40° C. for 2 hours. After the disappearance of the methyl 2-amino-3-chlorobenzoate was confirmed by HPLC analysis (area percentage method), 30 ml of toluene and 8.3 ml (80.8 mmol) of a 30% hydrogen peroxide solution were added to the reaction liquid, and 19.9 g (88.9 mmol) of a 25% aqueous potassium hydroxide solution was further added dropwise so that the temperature was 30° C. or less. The mixture was stirred at room temperature for 12 hours, and the reaction was completed. After the completion of the reaction, the methanol was distilled off, and 58 ml of toluene was added for separation. The obtained organic phase was washed with 20 ml of water, and methyl 3-chloro-2-nitrobenzoate was obtained as a toluene solution. This solution was analyzed by HPLC by the absolute calibration method, and as a result, the yield was 88%. The amount of the potassium hydroxide added is sufficient to make the pH condition alkaline.

Provenance & Evidence