Ethyl Propionate → HCID 22184688, Verbindung

HRID 968192Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 968192
C(NC(C)C)(C)C.C([Li])CCC.[CH2:13]([CH:15]([CH2:19][CH3:20])[CH2:16][C:17]#[N:18])[CH3:14].[C:21](OCC)(=[O:24])[CH2:22][CH3:23]>C1COCC1.CCCCCC>[C:17]([CH:16]([CH:15]([CH2:19][CH3:20])[CH2:13][CH3:14])[C:21](=[O:24])[CH2:22][CH3:23])#[N:18]

Komponenten

7

Edukt 4

HCID 7749Ethyl PropionateHCID 7912DiisopropylamineHCID 128361403-EthylpentanenitrileHCID 178418339Butyllithium

Produkt 1

HCID 22184688HCID 22184688, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittelHCID 8058HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Part B. A solution of diisopropylamine (7.50 mL, 57.2 mmol) in THF (100 mL) was cooled to −78° C., and treated with n-butyllithium (34.0 mL of a 1.6 M solution in hexane). The solution was warmed briefly to 0° C., and then recooled to −78° C. The nitrile compound from Part A was then added by syringe, and the solution was allowed to stir for 1 hour. Then, ethyl propionate (6.50 mL, 56.7 mmol) was added by syringe, and the resulting mixture was allowed to stir and warm to ambient temperature for 12 hours. It was poured into 200 mL of satd. aq. NH4Cl solution, and this was extracted with ethyl acetate (2×200 mL). The extracts were combined, dried over magnesium sulfate, filtered and evaporated. The residual oil was separated by column chromatography (silica gel, 10:90 ethyl acetate-hexane) to afford the product, 4-cyano-5-ethyl-3-heptanone, as an oil 4.06 g, 24.3 mmol, 49%). TLC RF 0.47 (20:80 ethyl acetate-hexane). Spectral data: 1H NMR (300 MHz, CDCl3): δ 3.49 (1H, d, J=4.4 Hz), 2.74 (2H, q, J=7.3 Hz), 2.08-1.98 (1H, m), 1.70-1.58 (1H, m), 1.50-1.20 (3H, m), 1.12 (3H, t, J=7.3 Hz), 0.95 (3H, t, J=7.3 Hz), 0.91 (3H, t, J=7.3 Hz). MS (H2O-GC/MS): m/e 167 (100).

Aufarbeitung

  1. customrecooled to −78° C
  2. stirringto stir
  3. temperaturewarm to ambient temperature for 12 hours
  4. additionIt was poured into 200 mL of satd
  5. extractionaq. NH4Cl solution, and this was extracted with ethyl acetate (2×200 mL)
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customThe residual oil was separated by column chromatography (silica gel, 10:90 ethyl acetate-hexane)

Quellen und Nachweise

ORD-Eintrag
ord-dfa59a98db9a46b681b8c4b22c728857
Quelldatensatz
uspto-grants-2005_10
Patentnummer
US06958341B2

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