Hydrochloric Acid → 2-(Hydroxyimino)-3-(2-nitrophenyl)propanoic acid

HRID 1462167

Reaktionsgleichung

Reaktionsgleichung von HRID 1462167
C[O-].[Na+].[N+:4]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[CH3:13])([O-:6])=[O:5].[C:14](OCC)(=O)[C:15]([O:17]CC)=[O:16].Cl.[NH2:25][OH:26].[OH-].[Na+].Cl>O.C(O)C>[N+:4]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[CH2:13][C:14](=[N:25][OH:26])[C:15]([OH:17])=[O:16])([O-:6])=[O:5]

Komponenten

9

Edukt 6

HCID 313Hydrochloric AcidHCID 69442-NitrotolueneHCID 7268Diethyl OxalateHCID 14798Sodium HydroxideHCID 443297Hydroxyamine hydrochlorideHCID 10942334Sodium Methoxide

Produkt 1

HCID 714366072-(Hydroxyimino)-3-(2-nitrophenyl)propanoic acid

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 702EthanolLösungsmittelHCID 962WaterLösungsmittel2×

Versuchsvorschrift

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).

Aufarbeitung

  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°)

Quellen und Nachweise

ORD-Eintrag
ord-0c630e29411d4580b4187f396ea07e97
Quelldatensatz
uspto-grants-1984_07
Patentnummer
US04459232

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