Diisopropylamine → Ethyl (E)-4-hydroxy-3-methyl-6-oxo-6-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthalenyl)-2-hexenoate

HRID 356724

Reaktionsgleichung

Reaktionsgleichung von HRID 356724
C(NC(C)C)(C)C.C([Li])CCC.CCCCCC.[C:19]([C:22]1[C:31]([CH3:32])=[CH:30][C:29]2[C:28]([CH3:34])([CH3:33])[CH2:27][CH2:26][C:25]([CH3:36])([CH3:35])[C:24]=2[CH:23]=1)(=[O:21])[CH3:20].[CH:37](/[C:39](/[CH3:46])=[CH:40]/[C:41]([O:43][CH2:44][CH3:45])=[O:42])=[O:38].[NH4+].[Cl-]>C1COCC1>[OH:38][CH:37]([CH2:20][C:19](=[O:21])[C:22]1[C:31]([CH3:32])=[CH:30][C:29]2[C:28]([CH3:34])([CH3:33])[CH2:27][CH2:26][C:25]([CH3:36])([CH3:35])[C:24]=2[CH:23]=1)/[C:39](/[CH3:46])=[CH:40]/[C:41]([O:43][CH2:44][CH3:45])=[O:42]

Komponenten

8

Edukt 6

HCID 7912DiisopropylamineHCID 8058HexaneHCID 25517Ammonium ChlorideHCID 87186Ethanone, 1-(5,6,7,8-tetrahydro-3,5,5,8,8-pentamethyl-2-naphthalenyl)-HCID 6009828Ethyl (2E)-3-methyl-4-oxo-2-butenoate2×HCID 178418339Butyllithium

Produkt 1

HCID 86749105Ethyl (E)-4-hydroxy-3-methyl-6-oxo-6-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthalenyl)-2-hexenoateAusbeute 80 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel3×

Versuchsvorschrift

To a solution of diisopropylamine (0.5 mL, 3.52 mmol) in 7 mL of THF at -78° C. under argon was added a 1.6M solution of n-butyllithium in hexane (2.2 mL, 3.52 mmol). The mixture was stirred for 25 min, and a solution of ketone 39 (0.78 g, 3.2 mmol) in 4 mL of THF was added slowly. The mixture was stirred for 20 min, and a solution of ethyl (E)-3-formyl-2-butenoate 40 (0.45 g, 3.2 mmol) (ethyl (E)-3-formyl-2-butenoate 40 is readily available from Fluka) in 3 mL of THF was added slowly. The mixture was stirred for 35 min at -78° C., poured into saturated aqueous NH4Cl, and extracted with 40% ethyl acetate/hexane. The combined organic layers were dried over anhydrous MgSO4, filtered, and concentrated to afford a light-yellow solid. Flash chromatography yielded the desired alcohol 41 as a white crystalline solid (0.98 g, 80%): m.p. 126°-128° C.; Rf 0.13 (10% ethyl acetate/hexane). The structure of the product was also confirmed using IR, 1H NMR and mass spectroscopy.

Aufarbeitung

  1. stirringThe mixture was stirred for 20 min
  2. additionwas added slowly
  3. stirringThe mixture was stirred for 35 min at -78° C.
  4. extractionextracted with 40% ethyl acetate/hexane
  5. dry with materialThe combined organic layers were dried over anhydrous MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto afford a light-yellow solid

Quellen und Nachweise

ORD-Eintrag
ord-5ded0d4ece2544ac996a3b2409c56032
Quelldatensatz
uspto-grants-1998_11
Patentnummer
US05837725

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