Chlorosulfonic acid → Methyl 8-nitro-4-oxo-4H-1-benzopyran-2-carboxylate

Participants

Reaction Conditions

Reaction Steps

A reaction container equipped with a stirrer, a cooling tube and a thermometer was charged with 300 parts by weight of chlorosulfonic acid. Thereto, 60 parts by weight of a mixture (content: 81.1% by weight, fumaric acid/maleic acid ratio=57/43) containing dimethyl 2-(2-nitrophenoxy)fumarate and dimethyl 2-(2-nitrophenoxy)maleate was added dropwise at an inner temperature of 50° C. or below. After completion of addition, the inner temperature was raised to 60° C. and the mixture was stirred and kept at the same temperature for 5 hours and at an inner temperature of 70° C. for 3 hours to obtain a reaction solution containing 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran (reaction yield: 86%). After cooled to room temperature, the reaction solution was poured gradually into 360 parts by weight of water. The mixture was kept at an inner temperature of 60° C. for 8 hours and then cooled to an inner temperature of 0° C. gradually. Precipitated crystals were filtered and dried to obtain 30 parts by weight of a crystalline mixture of 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran and 8-nitro-2-carboxy-4-oxo-4H-1-benzopyran (the content of 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran: 2.5% by weight; the content of 8-nitro-2-carboxy-4-oxo-4H-1-benzopyran: 96.7% by weight). The yield of 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran was 2% and the yield of 8-nitro-2-carboxy-4-oxo-4H-1-benzopyran was 73%.

Provenance & Evidence