N,N,N',N'-Tetramethylethylenediamine → HCID 85040365, Verbindung

HRID 258142

Reaktionsgleichung

Reaktionsgleichung von HRID 258142
CN(CCN(C)C)C.Br[C:10]1[CH:11]=[C:12]2[C:16](=[CH:17][CH:18]=1)[N:15]([CH3:19])[CH:14]1[N:20]([CH3:23])[CH2:21][CH2:22][C:13]21[CH3:24].[C:25](OCCCC)(=[O:33])[C:26]([O:28][CH2:29][CH2:30][CH2:31][CH3:32])=[O:27].[Cl-].[NH4+]>O1CCCC1>[O:33]=[C:25]([C:10]1[CH:11]=[C:12]2[C:16](=[CH:17][CH:18]=1)[N:15]([CH3:19])[CH:14]1[N:20]([CH3:23])[CH2:21][CH2:22][C:13]21[CH3:24])[C:26]([O:28][CH2:29][CH2:30][CH2:31][CH3:32])=[O:27]

Komponenten

6

Edukt 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 16306Dibutyl OxalateHCID 25517Ammonium ChlorideHCID 197825615-Bromo-1,2,3,3a,8,8a-hexahydro-1,3a,8-trimethylpyrrolo[2,3-b]indole

Produkt 1

HCID 85040365HCID 85040365, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

To a nitrogen purged 100 ml 3 neck round bottom flask was added anhydrous tetrahydrofuran (THF) (7.0 ml). Sec-butyllithium (1.3M in cyclohexane, 8.9 ml) was then added, the solution cooled to -78° C. and treated with TMEDA (1.6 ml; 11.0 mmol). A solution of 5-bromo-1,2,3,3a,8,8a-hexahydro-1,3a,8-trimethylpyrrolo[2,3-b]indole (2.50 g) in anhydrous THF (6.0 ml) was added via canula and the mixture stirred at -78° C. for 11/2 hours and -20° C. for 1 hour. The resulting solution was then added via canula to a solution of freshly distilled dibutyl oxalate (5.5 ml) in THF (9.0 ml) at -78° C. and maintained at this temperature with stirring for 1 hour. After allowing the mixture to slowly come to room temperature, saturated ammonium chloride solution (10 ml) was added and the solvent removed under reduced pressure. The product was purified by preparative HPLC (silica gel, eluted with 10% methanol in ethyl acetate). The appropriate fractions were combined and evaporated to give 0.51 g of an oil, which upon trituration with hexane afforded 1,2,3,3a,8,8a-hexahydro-α-oxo-1,3a,8-trimethyl-5-pyrrolo[2,3]-indole acetic acid, n-butyl ester, as a solid, m.p. 56°-61° C.

Aufarbeitung

  1. customTo a nitrogen purged 100 ml 3 neck round bottom flask
  2. additionwas added anhydrous tetrahydrofuran (THF) (7.0 ml)
  3. additionSec-butyllithium (1.3M in cyclohexane, 8.9 ml) was then added
  4. temperaturemaintained at this temperature
  5. stirringwith stirring for 1 hour
  6. customto slowly come to room temperature
  7. customthe solvent removed under reduced pressure
  8. customThe product was purified by preparative HPLC (silica gel, eluted with 10% methanol in ethyl acetate)
  9. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-2ee1753dc0f644019276a4e9e9ce19e1
Quelldatensatz
uspto-grants-1993_11
Patentnummer
US05264587

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