Methanol → 3-(1-Methylcyclopropyl)-3-oxopropanenitrile

HRID 729599Notes

Reaction equation

HRID 729599 reaction equation
[C:1](#[N:3])[CH3:2].[H-].[Na+].C[O:7][C:8]([C:10]1([CH3:13])[CH2:12][CH2:11]1)=O.CO>C1COCC1.O>[CH3:13][C:10]1([C:8](=[O:7])[CH2:2][C:1]#[N:3])[CH2:12][CH2:11]1

Participants

7

Reactant 4

HCID 887MethanolHCID 6342AcetonitrileHCID 24758Sodium hydrideHCID 543995Methyl 1-methylcyclopropane-1-carboxylate

Product 1

HCID 133930463-(1-Methylcyclopropyl)-3-oxopropanenitrile

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

Add acetonitrile (87 mL, 1.6 mol) to a suspension of sodium hydride (66 g, 1.6 mol) in THF (700 mL) at room temperature and stir 10 minutes. Then add 1-methyl-cyclopropanecarboxylic acid methyl ester (90.0 g, 0.78 mol) and reflux the white slurry for 3 hours. Cool the mixture, then add methanol (200 mL) and pour the mixture over water (500 mL). Separate the phases and reduce the pH of the aqueous phase with 1.0N HCl until pH 3-4. Extract the aqueous phase with diethyl ether (2×350 mL), combine the organic layers and wash with aqueous sodium chloride. Dry over sodium sulfate, filter, and concentrate under reduced pressure to give 3-(1-methyl-cyclopropyl)-3-oxo-propionitrile as yellow oil. 1H NMR (CDCl3): 3.59 (s, 2H), 1.37 (s, 3H), 1.30 (q, J=4 Hz, 2H), 0.86 (q, J=4 Hz, 2H).

Workup

  1. temperatureCool the mixture
  2. customSeparate the phases
  3. extractionExtract the aqueous phase with diethyl ether (2×350 mL)
  4. washwash with aqueous sodium chloride
  5. dry with materialDry over sodium sulfate
  6. filtrationfilter
  7. concentrationconcentrate under reduced pressure

Sources & evidence

ORD record
ord-39ef451c54f247d58e5c20559f8749d9
Source dataset
uspto-grants-2009_09
Patent number
US07582638B2

Reaction notes

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