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

HRID 1355906Notes

Reaction equation

HRID 1355906 reaction equation
[C:1](#[N:3])[CH3:2].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH3:14][C:15]1[O:19][C:18]([C:20](OC)=[O:21])=[CH:17][CH:16]=1.Cl>C1COCC1>[CH3:14][C:15]1[O:19][C:18]([C:20](=[O:21])[CH2:2][C:1]#[N:3])=[CH:17][CH:16]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6342AcetonitrileHCID 137628Methyl 5-methyl-2-furancarboxylateHCID 2733832Lithium Hexamethyldisilazide

Product 1

HCID 153240603-(5-Methylfuran-2-yl)-3-oxopropanenitrileYield 55.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-20 °C

Procedure

Following the method of Turner and Jacks (J. Org. Chem. 1989, 54, 4229), to a stirred solution of 5.6 ml (107 mmol) acetonitrile in 20 ml dry THF under argon at −78° C. was added dropwise 47.0 ml (47.09 mmol) lithium bis(trimethylsilyl)amide solution (1M in THF) and stirring continued for 30 minutes, after which a solution of 3.0 g (21.4 mmol) methyl 5-methyl-2-furoate in 20 ml THF was added dropwise and stirring continued while the reaction mixture was allowed to warm slowly to −20° C. The reaction mixture was then cannulated into a rapidly stirred solution of 1M hydrochloric acid at 0° C. The mixtured was extracted twice with ether and the combined organic phases dried over sodium sulfate and concentrated in vacuo. Chromatography (ethyl acetatephexane 1/1) afforded 1.77 g (55%) 3-(5-methyl-furan-2-yl)-3-oxo-propionitrile as a yellow crystalline solid. EI-MS m/e (%): 149 (M+, 24), 109 ([M—CH2CN]+, 100), 53 (30).

Workup

  1. stirringstirring
  2. extractionThe mixtured was extracted twice with ether
  3. dry with materialthe combined organic phases dried over sodium sulfate
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-1bfdfeb4b9874a8c9d1f96d8fd723d31
Source dataset
uspto-grants-2003_07
Patent number
US06586441B2

Reaction notes

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