Sodium hydride → Diethyl 2-fluoro-2-phenylmalonate

HRID 1633211

Reaktionsgleichung

Reaktionsgleichung von HRID 1633211
[C:1]1([CH:7]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[H-].[Na+].[H][H].[F:22]N(CC(C)(C)C)S(CCCC)(=O)=O>O1CCCC1.C1(C)C=CC=CC=1.CCOCC>[F:22][C:7]([C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:13]([O:15][CH2:16][CH3:17])=[O:14]

Komponenten

8

Edukt 4

HCID 24758Sodium hydrideHCID 66514Diethyl phenylmalonateHCID 13222564N-fluoro-N-neopentyl-n-butylsulfonamideHCID 178418361HCID 178418361, Verbindung

Produkt 1

HCID 4246642Diethyl 2-fluoro-2-phenylmalonateAusbeute 66,6 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 1140TolueneLösungsmittel2×HCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

Diethyl phenylmalonate (708 mg, 650 μL, 3 mmole) was dissolved in anhydrous tetrahydrofuran (5 mL) under nitrogen. Sodium hydride (144 mg as a 60% oil dispersion, 3.6 mmole) was added and the mixture was stirred until hydrogen evolution ceased (about 15 minutes). The solution was then diluted with anhydrous toluene (10 mL) and added dropwise to a solution of N-fluoro-N-neopentyl-n-butylsulfonamide (675 mg, 3 mmole) in anhydrous toluene (5 mL) and the mixture was stirred at room temperature under nitrogen. After 30 minutes the reaction mixture was diluted with ether (100 mL), washed with aqueous 1N oxalic acid (30 mL), 10% aqueous potassium bicarbonate (30 mL), and saturated aqueous sodium chloride (30 mL) solutions, and then dried over anhydrous magnesium sulfate. Filtration, removal of solvent under reduced pressure, and purification by flash column chromatography (silica, 1:1 methylene chloride-hexane) yielded diethyl 2-fluoro-2-phenylmalonate as a colorless liquid (508 mg). 1H NMR was consistent with the desired structure.

Aufarbeitung

  1. custom(about 15 minutes)
  2. washwashed with aqueous 1N oxalic acid (30 mL), 10% aqueous potassium bicarbonate (30 mL), and saturated aqueous sodium chloride (30 mL) solutions
  3. dry with materialdried over anhydrous magnesium sulfate
  4. filtrationFiltration, removal of solvent
  5. customunder reduced pressure, and purification by flash column chromatography (silica, 1:1 methylene chloride-hexane)

Quellen und Nachweise

ORD-Eintrag
ord-dbbcb9f26df64ca7bb35c3fdc0a55e86
Quelldatensatz
uspto-grants-1984_10
Patentnummer
US04479901

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