Water → Ethyl 2-cyano-4-(2-fluorophenyl)-4-oxobutanoate

HRID 1782202Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1782202
C(=O)([O-])[O-].[K+].[K+].[C:7]([CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])#[N:8].Br[CH2:16][C:17]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=1[F:25])=[O:18].O>CC(C)=O.C(OCC)(=O)C>[C:7]([CH:9]([CH2:16][C:17]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=1[F:25])=[O:18])[C:10]([O:12][CH2:13][CH3:14])=[O:11])#[N:8]

Komponenten

7

Edukt 4

HCID 962WaterHCID 7764Ethyl cyanoacetateHCID 11430Potassium CarbonateHCID 27374492-Bromo-2'-fluoroacetophenone

Produkt 1

HCID 66924657Ethyl 2-cyano-4-(2-fluorophenyl)-4-oxobutanoateAusbeute 100 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 180AcetoneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
45 °C

Versuchsvorschrift

To a solution of 2′-fluoroacetophenone (28.6 g) in ethyl acetate (400 mL) was added copper (II) bromide (92.6 g), and the mixture was heated under reflux for 4 hr. The reaction mixture was allowed to cool to room temperature and the insoluble material was filtered off. The filtrate was concentrated under reduced pressure to give crude 2-bromo-1-(2-fluorophenyl)ethanone (yield 90.5 g) as an oil. Potassium carbonate (88 g) was added to ethyl cyanoacetate (168 g), and the mixture was stirred at 45° C. for 1 hr. A solution (360 mL) of crude 2-bromo-1-(2-fluorophenyl)ethanone (90.5 g) in acetone was added dropwise over 20 min. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hr. Water (300 mL) and ethyl acetate (300 mL) were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with 10% aqueous sodium dihydrogen phosphate solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Excess ethyl cyanoacetate contained in the obtained oil was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate=20:1→4:1) to give the title compound as an oil (yield 64.0 g, yield about 100%).

Aufarbeitung

  1. additionAfter completion of the dropwise addition
  2. stirringthe mixture was stirred at the same temperature for 1 hr
  3. extractionthe mixture was extracted with ethyl acetate
  4. washThe extract was washed with 10% aqueous sodium dihydrogen phosphate solution and saturated brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customwas evaporated under reduced pressure
  8. customthe residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate=20:1→4:1)

Quellen und Nachweise

ORD-Eintrag
ord-e33a9ba343394335877606309aa8e11d
Quelldatensatz
uspto-grants-2009_03
Patentnummer
US07498337B2

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