Hydrochloric Acid → 3-[(4,4,4-Trifluoro-3-oxo-1-butenyl)amino]-2-propenenitrile

HRID 1744265Notes

Reaction equation

HRID 1744265 reaction equation
[H-].[Na+].[NH2:3][CH:4]=[CH:5][C:6](=[O:11])[C:7]([F:10])([F:9])[F:8].CO[CH:14]=[CH:15][C:16]#[N:17].Cl>CN(C)C=O.CCCCCC.C(OCC)(=O)C.O>[F:8][C:7]([F:10])([F:9])[C:6](=[O:11])[CH:5]=[CH:4][NH:3][CH:14]=[CH:15][C:16]#[N:17]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 27237553-Methoxy-2-propenenitrileHCID 27794423-Buten-2-one, 4-amino-1,1,1-trifluoro-, (3Z)-

Product 1

HCID 731022503-[(4,4,4-Trifluoro-3-oxo-1-butenyl)amino]-2-propenenitrileYield 52.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

Sodium hydride (60% dispersion in mineral oil, 400 mg, 10 mmol) was charged and washed with hexane twice. Into this flask, N,N-dimethylformamide (10 ml) was added and then a solution prepared by dissolving 4-amino-1,1,1-trifluoro-3-buten-2-one (1.4 g, 10 mmol) and 3-methoxyacrylonitrile (830 mg, 10 mmol) in N,N-dimethylformamide (5 ml) was added dropwise under ice-cooling. After stirring the mixture at room temperature for 3 hours, the reaction mixture was poured into water (50 ml). This mixture was acidified with concentrated hydrochloric acid under ice-cooling, and then extracted with ethyl acetate. The organic layers were combined, washed with brine, dried over magnesium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (an eluting solvent: hexane/ethyl acetate=3/1 to 1/1) to obtain 993 mg (yield 52.3%) of title compound (IIa) having a low polarity and 457 mg (yield 24.0%) of title compound (IIb) having a high polarity.

Workup

  1. washwashed with hexane twice
  2. additionInto this flask, N,N-dimethylformamide (10 ml) was added
  3. customa solution prepared
  4. additionwas added dropwise under ice-
  5. temperaturecooling
  6. temperaturecooling
  7. extractionextracted with ethyl acetate
  8. washwashed with brine
  9. dry with materialdried over magnesium sulfate
  10. concentrationconcentrated under reduced pressure
  11. customThe resulting residue was purified by silica gel column chromatography (an eluting solvent

Sources & evidence

ORD record
ord-073d6c45738d42c598fdafed9416e94c
Source dataset
uspto-grants-2006_03
Patent number
US07015236B2

Reaction notes

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