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

HRID 1744266Notes

Reaction equation

HRID 1744266 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>COCCOC.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 31.2%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolventHCID 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, 1,2-dimethoxyethane (20 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 1,2-dimethoxyethane (5 ml) was added dropwise under ice-cooling. After stirring the mixture at room temperature for 4 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 saturated brine, dried over magnesium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (a eluting solvent: hexane/ethyl acetate=3/1 to 1/1) to obtain 593 mg (yield 31.2%) of title compound (IIa) having a low polarity and 680 mg (yield 35.8%) of title compound (IIb) having a high polarity.

Workup

  1. washwashed with hexane twice
  2. additionInto this flask, 1,2-dimethoxyethane (20 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 saturated brine
  9. dry with materialdried over magnesium sulfate
  10. concentrationconcentrated under reduced pressure
  11. customThe resulting residue was purified by silica gel column chromatography (a eluting solvent

Sources & evidence

ORD record
ord-c81cdda694554f189f7f75d7103c3d66
Source dataset
uspto-grants-2006_03
Patent number
US07015236B2

Reaction notes

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