Chlorosulfonic acid → Methyl 6-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 79.3 parts by weight of chlorosulfonic acid and warmed to 60° C. Thereto 20.2 parts by weight of a mixture (content: 55.8% by weight, isomer ratio=52/48) containing dimethyl 2-(4-nitrophenoxy)fumarate and dimethyl 2-(4-nitrophenoxy)maleate was added at an inner temperature of 60° C. The inner temperature was raised to 100° C. and the mixture was stirred and kept at the same temperature for 6 hours to obtain a reaction solution containing 6-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran (reaction yield: 95%). The reaction solution was poured gradually into 120 parts by weight of water at 60° C. and the mixture was kept at an inner temperature of 60° C. for 1 hour and then cooled gradually to an inner temperature of 25° C. Precipitated crystals were filtered and dried to obtain 10.8 parts by weight of a crystalline mixture of 6-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran and 6-nitro-2-carboxy-4-oxo-4H-1-benzopyran (the content of 6-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran: 23.0% by weight; the content of 6-nitro-2-carboxy-4-oxo-4H-1-benzopyran: 58.5% by weight). The yield of 6-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran was 24.9% and the yield of 6-nitro-2-carboxy-4-oxo-4H-1-benzopyran was 58.5%.

Provenance & Evidence