N,N,N',N'-Tetramethylethylenediamine → 1,2,3,3a,8,8a-Hexahydro-alpha-oxo-1,3a,8-trimethyl-5-pyrrolo[2,3-b]indole acetic acid, diethyl amide

HRID 1681644

Reaktionsgleichung

Reaktionsgleichung von HRID 1681644
C([Li])(CC)C.CN(CCN(C)C)C.Br[C:15]1[CH:16]=[C:17]2[C:21](=[CH:22][CH:23]=1)[N:20]([CH3:24])[CH:19]1[N:25]([CH3:28])[CH2:26][CH2:27][C:18]21[CH3:29].[CH2:30]([N:32]([C:35](=[O:41])[C:36](OCC)=[O:37])[CH2:33][CH3:34])[CH3:31]>CCOCC>[CH2:30]([N:32]([CH2:33][CH3:34])[C:35](=[O:41])[C:36](=[O:37])[C:15]1[CH:16]=[C:17]2[C:21](=[CH:22][CH:23]=1)[N:20]([CH3:24])[CH:19]1[N:25]([CH3:28])[CH2:26][CH2:27][C:18]21[CH3:29])[CH3:31]

Komponenten

6

Edukt 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 138489Ethyl N,N-diethyloxamateHCID 197825615-Bromo-1,2,3,3a,8,8a-hexahydro-1,3a,8-trimethylpyrrolo[2,3-b]indoleHCID 178418400CID 53628100

Produkt 1

HCID 867464261,2,3,3a,8,8a-Hexahydro-alpha-oxo-1,3a,8-trimethyl-5-pyrrolo[2,3-b]indole acetic acid, diethyl amide

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel3×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

To a stirred (-78° C.) solution of sec-butyllithium (1.3M in cyclohexane; 6.6 ml) and TMEDA (1.3 ml) in anhydrous ether (4.0 ml) was added via canula under a N2 atmosphere a solution of 5-bromo-1,2,3,3a,8,8a-hexahydro-1,3a,8-trimethylpyrrolo[2,3-b]indole (1.69 g), in anhydrous ether (4.0 ml). The solution was stirred at -78° C. for 2.5 hours and then added via canula, under N2, to a stirred (-78° C.) solution of N,N-diethylamino-oxo-acetic acid, ethyl ester (3.6 g) in diethyl ether (8.0 ml). The solution was stirred at -78° C. for 3 hours and gradually allowed to warm to room temperature over 2 hours. The mixture was quenched by the addition of an aqueous solution of saturated NH4Cl. The organic phase was separated and washed with two 50 ml portions of an aqueous solution of saturated NaHCO3, with brine, and dried (Na2SO 4). The crude residue was purified using preparative HPLC (silica gel, loading and eluting with 3% methanol in dichloromethane). The appropriate fractions were combined and concentrated to a foam which solidied upon trituration with hexane, to afford 1,2,3,3a,8,8a-hexahydro-α-oxo-1,3a,8-trimethyl-5-pyrrolo[2,3-b]indole acetic acid, diethyl amide.

Aufarbeitung

  1. additionadded via canula, under N2
  2. stirringThe solution was stirred at -78° C. for 3 hours
  3. temperatureto warm to room temperature over 2 hours
  4. customThe mixture was quenched by the addition of an aqueous solution of saturated NH4Cl
  5. customThe organic phase was separated
  6. washwashed with two 50 ml portions of an aqueous solution of saturated NaHCO3, with brine
  7. dry with materialdried (Na2SO 4)
  8. customThe crude residue was purified
  9. washHPLC (silica gel, loading and eluting with 3% methanol in dichloromethane)
  10. concentrationconcentrated to a foam which

Quellen und Nachweise

ORD-Eintrag
ord-656d73a91c444ca3b6f0cfdcd4a648e3
Quelldatensatz
uspto-grants-1992_12
Patentnummer
US05173497

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