2-Aminophenol → HCID 20431560, compound

Participants

Reaction Steps

A mixture of 21.8 g. (0.2 mole) of o-aminophenol and 31.6 g. (0.2 mole) of dimethyl itaconate in a 500 ml. round bottomed flask was heated to 190° for 1 hr. and volatile by-products were allowed to escape. The residue was taken up in 150 ml. of boiling EtOAc and diluted with 300 ml. of (i-Pr)2O. After the solution had cooled, it was clarified by filtration, evaported to a volume of 100 ml., and chilled at 5°. The tan crystalline solid was collected on a filter, and dried in air to give 22 g. of crude hydroxy ester, m.p. 120°-124°. Conversion of 5.0 g. (0.0212 mole) of the foregoing hydroxy ester was accomplished by stirring with 50 ml. of concentrated NH4OH at 25° for 24 hrs. Volatile material was removed by distillation at 95°/50 mm and the red glassy residue was taken up in a small amount of EtOAc-MeOH and allowed to stand. Crystals were deposited on standing. They were collected, and recrystallized from i-PrOH-EtOAc to give 3.12 g. of the desired product, m.p. 133°-135°, which was further purified by recrystallization from CH3CN using activated carbon, yield 1.9 g. m.p. 135°-138°. This material was used without further purification as starting material for Procedure 6.

Provenance & Evidence