Water → Diallyl {2-[1-(2-ethoxy-2-oxoethyl)cyclopropyl]ethyl}[4-(methoxycarbonyl)benzyl]malonate

HRID 1920581Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1920581
[H-].[Na+].[CH3:3][O:4][C:5]([C:7]1[CH:26]=[CH:25][C:10]([CH2:11][CH:12]([C:19]([O:21][CH2:22][CH:23]=[CH2:24])=[O:20])[C:13]([O:15][CH2:16][CH:17]=[CH2:18])=[O:14])=[CH:9][CH:8]=1)=[O:6].Br[CH2:28][CH2:29][C:30]1([CH2:33][C:34]([O:36][CH2:37][CH3:38])=[O:35])[CH2:32][CH2:31]1.O>CN(C=O)C.C(OCC)(=O)C>[CH2:37]([O:36][C:34](=[O:35])[CH2:33][C:30]1([CH2:29][CH2:28][C:12]([CH2:11][C:10]2[CH:9]=[CH:8][C:7]([C:5]([O:4][CH3:3])=[O:6])=[CH:26][CH:25]=2)([C:19]([O:21][CH2:22][CH:23]=[CH2:24])=[O:20])[C:13]([O:15][CH2:16][CH:17]=[CH2:18])=[O:14])[CH2:31][CH2:32]1)[CH3:38]

Komponenten

7

Edukt 4

HCID 962WaterHCID 24758Sodium hydrideHCID 57831347Diallyl [4-(methoxycarbonyl)benzyl]malonateHCID 57965767Ethyl [1-(2-bromoethyl)cyclopropyl]acetate

Produkt 1

HCID 57965758Diallyl {2-[1-(2-ethoxy-2-oxoethyl)cyclopropyl]ethyl}[4-(methoxycarbonyl)benzyl]malonate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6228DimethylformamideLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

Under argon and at 0° C., 1.67 g (41.62 mmol) of sodium hydride (60% strength dispersion in mineral oil) are added a little at a time to a solution of 10.87 g (32.70 mmol) of diallyl [4-(methoxycarbonyl)benzyl]malonate in 60 ml of anhhdrous DMF. The mixture is stirred at 40° C. for 30 min, and a solution of 6.99 g (29.73 mmol) of ethyl [1-(2-bromoethyl)cyclopropyl]acetate in 60 ml of anhydrous DMF is then added dropwise at this temperature. The reaction mixture is subsequently heated at 100° C. for 8 hours. After addition of 600 ml of water and 200 ml of ethyl acetate and phase separation, the aqueous phase is extracted twice with ethyl acetate. The organic phase is then washed five times with water and once with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The crude product is initially purified by flash chromatography (400 g of silica gel 60, mobile phase: cyclohexane/ethyl acetate 4:1), and then by preparative HPLC. This gives 4.87 g (28% of theory) of the title compound in the form of a colorless oil.

Aufarbeitung

  1. temperatureThe reaction mixture is subsequently heated at 100° C. for 8 hours
  2. extractionthe aqueous phase is extracted twice with ethyl acetate
  3. washThe organic phase is then washed five times with water
  4. dry with materialonce with saturated sodium chloride solution and dried over anhydrous magnesium sulfate
  5. customThe crude product is initially purified by flash chromatography (400 g of silica gel 60, mobile phase: cyclohexane/ethyl acetate 4:1)

Quellen und Nachweise

ORD-Eintrag
ord-a93f0ab78b574807b78dcc7594c08227
Quelldatensatz
uspto-grants-2012_05
Patentnummer
US08168821B2

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