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 250 parts by weight of chlorosulfonic acid. Thereto, 50 parts by weight of a mixture (content: 82.1% by weight, fumaric acid/maleic acid ratio=58/42) of 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 70° C. and the mixture was stirred and kept at the same temperature for 6 hours to obtain a reaction solution containing 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran (reaction yield: 92%). After cooled to room temperature, the reaction solution was gradually added into 300 parts by weight of water. The mixture was kept at an inner temperature of 60° C. for 1 hour and then gradually cooled to an inner temperature of 0° C. 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: 58.5% by weight; the content of 8-nitro-2-carboxy-4-oxo-4H-1-benzopyran: 39.8% by weight). The yield of 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran was 32% and the yield of 8-nitro-2-carboxy-4-oxo-4H-1-benzopyran was 50%.

Provenance & Evidence