Hydrochloric Acid → 3-(5-Bromofuran-2-yl)-3-oxopropanenitrile

HRID 1356128Notes

Reaction equation

HRID 1356128 reaction equation
[H-].[Na+].[C:3](#[N:5])[CH3:4].C[O:7][C:8]([C:10]1[O:11][C:12]([Br:15])=[CH:13][CH:14]=1)=O.Cl>C1COCC1>[Br:15][C:12]1[O:11][C:10]([C:8](=[O:7])[CH2:4][C:3]#[N:5])=[CH:14][CH:13]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6342AcetonitrileHCID 24758Sodium hydrideHCID 599633Methyl 5-bromofuran-2-carboxylate

Product 1

HCID 133193593-(5-Bromofuran-2-yl)-3-oxopropanenitrileYield 75%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To 1.95 g (48.8 mmol, 60% dispersion in mineral oil) sodium hydride in a 2-necked flask fitted with a reflux condenser was added dropwise 30 ml THF and the mixture was then heated to reflux. A solution of 6.4 ml (122 mmol) acetonitrile and 5.00 g (24.4 mmol) 5-bromo-furan-2-carboxylic acid methyl ester in 20 ml dry THF was added dropwise and the reaction mixture heated at reflux for 5 hours. The reaction mixture was then cannulated into a rapidly stirred solution of 1M hydrochloric acid at 0° C. The mixture was extracted twice with ethyl acetate and the combined organic phases dried over sodium sulfate and concentrated in vacuo. Chromatography (ethyl acetate/hexane 2/3) afforded 3.90 g (75%) 3-(5-bromo-furan-2-yl)-3-oxo-propionitrile as a yellow crystalline solid. EI-MS m/e (%): 215 (M{81Br}+, 27), 213 (M{79Br}+, 28), 175 ([M{81Br}—CH2CN]+, 100), 173 ([M{79Br}—CH2CN]+, 100), 38 (59).

Workup

  1. temperaturethe mixture was then heated to reflux
  2. temperaturethe reaction mixture heated
  3. temperatureat reflux for 5 hours
  4. extractionThe mixture was extracted twice with ethyl acetate
  5. dry with materialthe combined organic phases dried over sodium sulfate
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-8e91c2f6a23f4e259e12da757cfcc676
Source dataset
uspto-grants-2003_07
Patent number
US06586441B2

Reaction notes

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