Diethyl Malonate → Diethyl 2-pent-4-enylpropanedioate

HRID 131117

Reaktionsgleichung

Reaktionsgleichung von HRID 131117
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].Br[CH2:15][CH2:16][CH2:17][CH:18]=[CH2:19]>CN(C=O)C>[CH2:12]([O:11][C:3](=[O:10])[CH:4]([CH2:19][CH2:18][CH2:17][CH:16]=[CH2:15])[C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH3:13]

Komponenten

5

Edukt 3

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 707041-Pentene, 5-bromo-

Produkt 1

HCID 361718Diethyl 2-pent-4-enylpropanedioateAusbeute 101,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A mixture of sodium hydride (60% in mineral oil, 2.4 g, 60.5 mmol, 1.1 eq) and diethyl malonate (8.34 mL, 55 mmol, 1 eq) in DMF (200 mL) was cooled to 0° C. and 5-bromo-1-pentene (6.5 mL, 55 mmol, 1 eq) was added dropwise. The reaction mixture was warmed to rt, stirred for 14 hours and then partitioned between ether and water. The layers were separated, the aqueous layer was extracted with ether (2×250 mL) and the combined organic phases were washed with water (2×) and brine, dried over MgSO4 and concentrated to give E1.1 as a colorless oil (12.7 g, 100% yield). 1H NMR (400 MHz, CDCl3): δ 5.71 (m, 1 H), 4.92 (m, 2 H), 4.12 (q, J=7.1 Hz, 4 H), 3.25 (t, J=7.58 Hz, 1 H), 2.01 (m, 2 H), 1.83 (m, 2 H), 1.36 (m, 2 H), 1.20 (t, J=7.1 Hz, 6 H).

Aufarbeitung

  1. temperatureThe reaction mixture was warmed to rt
  2. custompartitioned between ether and water
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with ether (2×250 mL)
  5. washthe combined organic phases were washed with water (2×) and brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-f51d1ade8be545a5945de7e438e9c56f
Quelldatensatz
uspto-grants-2008_06
Patentnummer
US07384937B2

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