Sulfuric 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 50.2 parts by weight of chlorosulfonic acid. Thereto, 25.0 parts by weight of 98% sulfuric acid was added dropwise over 1 hour and the mixture was then warmed to 60° C. Thereto, 25.3 parts by weight of the mixture (content: 89.6% by weight, fumaric acid/maleic acid ratio=54/46) containing dimethyl 2-(2-nitrophenoxy)fumarate and dimethyl 2-(2-nitrophenoxy)maleate obtained in Example 10 was added dropwise at an inner temperature of 60° C. over 4 hours. After completion of addition, the inner temperature was raised to 95° C. and the mixture was stirred and kept at the same temperature for 4 hours to obtain a reaction solution containing 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran (reaction yield: 88%). The reaction solution was poured gradually into 113 parts by weight of water at 85° C. or below. The mixture was kept at an inner temperature of 85° C. for 6 hours and then cooled gradually to an inner temperature of 25° C. Precipitated crystals were filtered and dried to obtain 16.3 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: 13.8% by weight; the content of 8-nitro-2-carboxy-4-oxo-4H-1-benzopyran: 84.6% by weight). The yield of 8-nitro-2-methoxycarbonyl-4-oxo-4H-1-benzopyran was 11.5% and the yield of 8-nitro-2-carboxy-4-oxo-4H-1-benzopyran was 74.0%.

Provenance & Evidence