Hydrogen Peroxide → Methyl 3-chloro-2-nitrobenzoate

Participants

Reaction Conditions

Reaction Steps

A solution of 7.1 g (28.5 mmol) of tungstic acid, 4.9 g (48.5 mmol) of concentrated sulfuric acid, 35.6 g (190 mmol) of methyl 2-amino-3-chlorobenzoate, and 6.9 g (19 mmol) of tetrabutylammonium hydrogen sulfate in 74 ml of chlorobenzene was heated to 47° C., and 50 ml (570 mmol) of a 35% hydrogen peroxide solution was added dropwise over 10 hours. The pH value at this time was 0.3. After the completion of the dropwise addition, the mixture was stirred at 47° C. for 4 hours. After the disappearance of the methyl 2-amino-3-chlorobenzoate was confirmed by HPLC analysis (area percentage method), 243 g (2.06 mol) of chlorobenzene and 19 g (150 mmol) of a 25% aqueous sodium hydroxide solution were added. The pH value at this time was 7.5. The reaction liquid was separated at 75° C., and 91 g of the aqueous layer was removed. Then, the obtained organic layer was cooled to 60° C. or less. 5.2 g (61.9 mmol) of sodium hydrogen carbonate and 5.2 ml of water were added, and 25 ml (285 mmol) of a 35% hydrogen peroxide solution was added dropwise while the reaction temperature was adjusted to 60° C. or less. After the completion of the dropwise addition, the mixture was stirred at 60° C. for 2 hours, and the reaction was completed. The reaction liquid was separated at room temperature. The obtained organic layer was analyzed by HPLC by the absolute calibration method, and as a result, the yield was 72%.

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