Trifluoroacetic acid → Ethyl 1-benzyl-3-cyanopyrrolidine-3-carboxylate

HRID 1618957

Reaktionsgleichung

Reaktionsgleichung von HRID 1618957
C(O)(C(F)(F)F)=O.[C:8]([C:10](=[CH2:16])[C:11]([O:13][CH2:14][CH3:15])=[O:12])#[N:9].[CH2:17]([N:24]([CH2:28][Si](C)(C)C)[CH2:25]OC)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>C(Cl)Cl>[CH2:17]([N:24]1[CH2:25][CH2:16][C:10]([C:8]#[N:9])([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:28]1)[C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1

Komponenten

5

Edukt 3

HCID 6422Trifluoroacetic acidHCID 81530Ethyl cyanoacrylateHCID 353442Benzyl(methoxymethyl)((trimethylsilyl)methyl)amine

Produkt 1

HCID 67228450Ethyl 1-benzyl-3-cyanopyrrolidine-3-carboxylateAusbeute 94 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

TFA (4.31 mmol, 0.49 g) was added to a solution of ethyl 2-cyanoacrylate (17.58 mmol, 2.20 g) in DCM (100 mL) under nitrogen atmosphere. Subsequently, a solution of N-benzyl-1-methoxy-N-((trimethylsilyl)methyl)methanamine (21.49 mmol, 5.10 g) in DCM (50 mL) was added dropwise while cooling with an ice-bath in order to keep the reaction temperature at room temperature (exothermic reaction). The reaction mixture was stirred overnight at room temperature. Then the mixture was washed with saturated aqueous NaHCO3 (100 mL). The aqueous phase was extracted with DCM (100 mL). The combined organic phase was dried over MgSO4 and evaporated in vacuo. The crude product was purified by flash silicagel chromatography (100% heptane to 50% EtOAc) yielding 4.27 g of a colorless oil (94%). 1H-NMR (400 MHz, CDCl3, 300K): δ=1.32 (3H, t, J=7.1 Hz), 2.44 (1H, m), 2.59 (1H, m), 2.69 (1H, m), 2.89 (1H, m), 2.99 (1H, d, J=9.8 Hz), 3.17 (1H, d, J=9.8 Hz), 3.69 (2H, s), 4.27 (2H, q, J=7.1 Hz), 7.29 (5H, m).

Aufarbeitung

  1. temperaturewhile cooling with an ice-bath in order
  2. customat room temperature
  3. custom(exothermic reaction)
  4. washThen the mixture was washed with saturated aqueous NaHCO3 (100 mL)
  5. extractionThe aqueous phase was extracted with DCM (100 mL)
  6. dry with materialThe combined organic phase was dried over MgSO4
  7. customevaporated in vacuo
  8. customThe crude product was purified by flash silicagel chromatography (100% heptane to 50% EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-e83238cfeb92442da7de8250fe822996
Quelldatensatz
uspto-grants-2014_07
Patentnummer
US08772286B2

Verknüpfte Notizen

Wird geladen…