反应详情

Absolute ethanol (24,000 ml) and 3,240 g (60.0 moles) of sodium methoxide were charged into a 20 gallon reaction flask. The solution was stirred under nitrogen while a solution of 8228.4 g (60.0 moles) of o-nitrotoluene and 8768.4 g (60.0 moles) of diethyl oxalate was added all at once. The resulting solution was heated at reflux for 25 minutes, cooled to 60° with an ice-bath and 18,000 ml of water were cautiously added. Heat was then applied and the mixture was held at the reflux temperature for 1 hour. Most of the ethanol was then removed. The turbid solution was cooled at 50° and a solution of 4,140 g (59.6 moles) of hydroxylamine hydrochloride in 6,000 ml of water was added all at once. The temperature was maintained at 50°, the pH was adjusted to 7.0 with 6,000 ml of 10N sodium hydroxide solution and the reaction mixture stirred overnight at ambient temperature. The suspension was cooled to 10° and the pH was adjusted to 1.0 with 6,000 ml of 12N hydrochloric acid. The stirring was continued overnight at 10° to complete the liberation of the free acid. The solid was collected, washed with 6×4,000 ml of water, air dried overnight and suspended in 20,000 ml of toluene. The suspension was stirred for 1 hour under nitrogen atmosphere. The product was collected, washed with 4×2,000 ml of toluene followed by 4×2,000 ml of petroleum ether and dried (5 mm Hg/60° ) to give 2-nitrophenylpyruvic acid oxime, m.p. 158°-60° (dec).

1. additionwas added all at once
2. temperatureThe resulting solution was heated
3. temperatureat reflux for 25 minutes
4. temperaturecooled to 60° with an ice-bath
5. temperatureHeat
6. customMost of the ethanol was then removed
7. temperatureThe turbid solution was cooled at 50°
8. temperatureThe temperature was maintained at 50°
9. temperatureThe suspension was cooled to 10°
10. waitThe stirring was continued overnight at 10°
11. customThe solid was collected
12. washwashed with 6×4,000 ml of water, air
13. customdried overnight
14. stirringThe suspension was stirred for 1 hour under nitrogen atmosphere
15. customThe product was collected
16. washwashed with 4×2,000 ml of toluene
17. customdried (5 mm Hg/60° )