Methyl acetoacetate → 5,6-Dihydro-4-hydroxy-6-phenyl-6-propyl-2H-pyran-2-one

HRID 481851

Reaktionsgleichung

Reaktionsgleichung von HRID 481851
[C:1]([O:7][CH3:8])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[H-].[Na+].[CH2:11]([Li])[CH2:12][CH2:13]C.C([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)(=O)CCC.[NH4+].[Cl-]>CCCCCC.O1CCCC1>[OH:4][C:3]1[CH2:5][C:8]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)([CH2:11][CH2:12][CH3:13])[O:7][C:1](=[O:6])[CH:2]=1

Komponenten

8

Edukt 5

HCID 7757Methyl acetoacetateHCID 10315ButyrophenoneHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

Produkt 1

HCID 547080065,6-Dihydro-4-hydroxy-6-phenyl-6-propyl-2H-pyran-2-one

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittelHCID 8058HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

The title compound was prepared as described in the General Method 1 using 5 mmol of methyl acetoacetate, 5.5 mmol of NaH 60% dispersion in oil, 5.5 mmol of 1.6M n-butyl lithium in hexane, 5.5 mmol of butyrophenone and 14 mL of tetrahydrofuran. After addition of the ketone, the reaction was stirred for 90 minutes at 0° C. The reaction was poured into saturated NH4Cl solution and extracted with ethyl acetate. The organic layer was dried over MgSO4, concentrated, and the residue flash chromatographed using hexane/ethyl acetate 80/20 as eluent. The aldol product was stirred at room temperature in 100 mL of 0.1N NaOH for 3.5 hours. The reaction was worked up as in General Method 1 and the product triturated from diethyl ether to afford a solid (m.p. 131.5°-132° C.). 1H NMR (CDCl3) δ0.88 (t, 3H), 1.1-1.4 (m, 2H), 1.95 (m, 2H), 2.90 (d, 1H), 2.92 (d, 1H), 3.25 (d, 1H), 3.35 (d, 1H), 7.2-7.4 (m, 5H).

Aufarbeitung

  1. extractionextracted with ethyl acetate
  2. dry with materialThe organic layer was dried over MgSO4
  3. concentrationconcentrated
  4. customthe residue flash chromatographed
  5. stirringThe aldol product was stirred at room temperature in 100 mL of 0.1N NaOH for 3.5 hours
  6. customthe product triturated from diethyl ether

Quellen und Nachweise

ORD-Eintrag
ord-adb45a93712b42b5979aca8328a8e04b
Quelldatensatz
uspto-grants-1998_08
Patentnummer
US05789440

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