Ethyl Propionate → HCID 22184688, compound

HRID 968192Notes

Reaction equation

HRID 968192 reaction equation
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]

Participants

7

Reactant 4

HCID 7749Ethyl PropionateHCID 7912DiisopropylamineHCID 128361403-EthylpentanenitrileHCID 178418339Butyllithium

Product 1

HCID 22184688HCID 22184688, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-dfa59a98db9a46b681b8c4b22c728857
Source dataset
uspto-grants-2005_10
Patent number
US06958341B2

Reaction notes

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