Diisopropylamine → 3-[2(R)-Benzyl-3-(benzyloxycarbonyl)propionyl]-4(S)-isopropyl-2-oxazolidinone

HRID 1768857Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1768857
C([Li])CCC.C(NC(C)C)(C)C.[CH:13]([C@H:16]1[CH2:20][O:19][C:18](=[O:21])[N:17]1[C:22](=[O:31])[CH2:23][CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)([CH3:15])[CH3:14].Br[CH2:33][C:34]([O:36][CH2:37][C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)=[O:35].[Cl-].[NH4+]>CCCCCC.O1CCCC1>[CH2:24]([C@H:23]([CH2:33][C:34]([O:36][CH2:37][C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)=[O:35])[C:22]([N:17]1[C@@H:16]([CH:13]([CH3:15])[CH3:14])[CH2:20][O:19][C:18]1=[O:21])=[O:31])[C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1

Komponenten

8

Edukt 5

HCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 62576Benzyl bromoacetateHCID 10467835(S)-4-isopropyl-3-(3-phenylpropanoyl)oxazolidin-2-oneHCID 178418339Butyllithium

Produkt 1

HCID 144294593-[2(R)-Benzyl-3-(benzyloxycarbonyl)propionyl]-4(S)-isopropyl-2-oxazolidinoneAusbeute 74 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittel

Versuchsvorschrift

22.50 ml (36.0 mmole) of butyllithium (as a 1.6M solution in hexane) were added dropwise, at -78° C. and under an atmosphere of nitrogen, to a solution of 5.05 ml (36.0 mmole) of diisopropylamine in 100 ml of anhydrous tetrahydrofuran, and the mixture was stirred for 30 minutes. At the end of this time, a solution of 7.84 g (30.0 mmole) of 4(S)-isopropyl-3-(3-phenyl-1-oxopropyl)-2-oxazolidinone (prepared as described in Preparation 12) in 50 ml of anhydrous tetrahydrofuran was added dropwise to the mixture. The mixture was then stirred for 1 hour, after which 14.26 ml (90.0 mmole) of benzyl bromoacetate were added to it. The mixture was stirred for 6 hours while the temperature of the reaction mixture was permitted to revert to room temperature. At the end of this time, the reaction mixture was mixed with a saturated aqueous solution of ammonium chloride and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was stripped from it by distillation under reduced pressure. The residue was purified by medium pressure column chromatography through silica gel (using a 1:3 by volume mixture of ethyl acetate and hexane as the eluent), followed by recrystallization from diisopropyl ether, to afford 9.05 g (yield 74%) of the title compound as white crystals, melting at 118°-120° C.

Aufarbeitung

  1. stirringThe mixture was then stirred for 1 hour
  2. stirringThe mixture was stirred for 6 hours while the temperature of the reaction mixture
  3. customto revert to room temperature
  4. extractionextracted with ethyl acetate
  5. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  6. distillationthe solvent was stripped from it by distillation under reduced pressure
  7. customThe residue was purified by medium pressure column chromatography through silica gel (
  8. additionby volume mixture of ethyl acetate and hexane as the eluent),
  9. customfollowed by recrystallization from diisopropyl ether

Quellen und Nachweise

ORD-Eintrag
ord-c67bf3ba6c4c40c3996ae443f0ba1932
Quelldatensatz
uspto-grants-1995_01
Patentnummer
US05378689

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