Acrylonitrile → Methyl 4-cyano-2-(2-fluoro-4-nitrophenyl)butanoate

HRID 1504958Notes

Reaction equation

HRID 1504958 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH:11]([C:16](OC)=O)[C:12]([O:14][CH3:15])=[O:13].[C:20](#[N:23])[CH:21]=C.CO[Na]>CO>[C:20]([CH2:21][CH2:16][CH:11]([C:3]1[CH:4]=[CH:5][C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]=1[F:1])[C:12]([O:14][CH3:15])=[O:13])#[N:23]

Participants

5

Reactant 3

HCID 7855AcrylonitrileHCID 53429620Dimethyl 2-(2-fluoro-4-nitrophenyl)malonateHCID 178418582HCID 178418582, compound

Product 1

HCID 68292723Methyl 4-cyano-2-(2-fluoro-4-nitrophenyl)butanoateYield 64.9%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of compound 65 (3 g, 11 mmol) and acrylonitrile (3.2 mL, 51 mmol) in absolute CH3OH (50 mL) was added a catalytic amount of CH3ONa (71 mg, 1.32 mmol) at room temperature with stirring under N2. The mixture was stirred at room temperature for overnight under N2. The mixture was diluted with aqNaHCO3 and extracted with DCM. The combined organic layers were washed with brine, dried over Na2SO4, concentrated and purified with silica gel column chromatography (PE:EtOAc=5:1) to give compound 66 (1.9 g, 64%) as a light yellow solid.

Workup

  1. stirringThe mixture was stirred at room temperature for overnight under N2
  2. additionThe mixture was diluted with aqNaHCO3
  3. extractionextracted with DCM
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. custompurified with silica gel column chromatography (PE:EtOAc=5:1)

Sources & evidence

ORD record
ord-bf1bfaab57364bc6a5a8de866438ea43
Source dataset
uspto-grants-2015_12
Patent number
US09216957B2

Reaction notes

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