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

HRID 513101

Reaktionsgleichung

Reaktionsgleichung von HRID 513101
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-0aaf70cd05724761ae627649c8ebb687
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09102676B2

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