Water → 4-Hydroxy-3-nitrobenzonitrile

Participants

Reaction Steps

A mixture of 5.0 g of 4-hydroxy-3-nitrobenzaldehyde with 2.5 g of hydroxylamine hydrochloride and 3.6 g of sodium formate was heated under reflux in 35 ml of formic acid for 5 hours. After the reaction mixture was cooled, water was added thereto. The precipitated crystal was collected by filtration to give 4.3 g of 4-hydroxy-3-nitrobenzonitrile. 3.5 g of thioacetamide was added thereto and the mixture was heated at 80° C. for 1 hour in 12 ml of N,N-dimethylformamide saturated with hydrochloric acid. After the completion of the reaction, the reaction mixture was neutralized with 30 ml of water and 18 ml of 2N sodium hydroxide. The precipitated crystal was collected by filtration and recrystallized from ethanol to give 3.9 g of 4-hydroxy-3-nitrobenzthioamide. This product was dissolved in 30 ml of ethanol, 2.7 g of ethyl 2-chloroacetoacetate was added thereto, and the mixture was heated under reflux for 5 hours. The reaction mixture was cooled, and the precipitated crystal was collected by filtration and recrystallized from ethanol to give 3.4 g of ethyl 2-(4-hydroxy-3-nitrophenyl)-4-methyl-5-thiazolecarboxylate (yield: 37%).

Provenance & Evidence