Cyanoacetic acid → HCID 367315, compound

HRID 1629976Notes

Reaction equation

HRID 1629976 reaction equation
[C:1]([CH2:3][C:4](O)=O)#[N:2].[F:7][C:8]1[CH:9]=[C:10]([CH:13]=[CH:14][CH:15]=1)C=O>C1(C)C=CC=CC=1.N1C=CC=CC=1>[F:7][C:8]1[CH:15]=[C:14]([CH:4]=[CH:3][C:1]#[N:2])[CH:13]=[CH:10][CH:9]=1

Participants

5

Reactant 2

HCID 9740Cyanoacetic acidHCID 680093-Fluorobenzaldehyde

Product 1

HCID 367315HCID 367315, compoundYield 80.2%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 1140TolueneSolvent

Procedure

A mixture of 35.0 g (411 mmol) of cyanoacetic acid (CAS 372-09-8) and 56.2 g (453 mmol) of 3-fluorobenzaldehyde (CAS 456-48-4) in a mixture of 400 ml of toluene and 220 ml of pyridine is refluxed for 22 hours using Dean-Stark apparatus to remove the water formed during the reaction. The solvent is then removed under reduced pressure and the residue is co-evaporated 3 times with toluene. The residue is then taken up in ethyl acetate and the organic phase is washed successively with aqueous 1N sodium hydroxide solution, aqueous 1N hydrochloric acid solution and then with saturated sodium chloride solution. The organic phase is then dried over sodium sulfate and the solvent is evaporated off under reduced pressure to give a brown oil, which is chromatographed on a column of silica gel, eluting with toluene, to give 48.5 g a mixture of (E) and (Z) 3-(3-fluorophenyl)-2-propenenitrile in a ratio of (7/3)

Workup

  1. temperatureis refluxed for 22 hours
  2. customto remove the water
  3. customformed during the reaction
  4. customThe solvent is then removed under reduced pressure
  5. washthe organic phase is washed successively with aqueous 1N sodium hydroxide solution, aqueous 1N hydrochloric acid solution
  6. dry with materialThe organic phase is then dried over sodium sulfate
  7. customthe solvent is evaporated off under reduced pressure
  8. customto give a brown oil, which
  9. customis chromatographed on a column of silica gel
  10. washeluting with toluene

Sources & evidence

ORD record
ord-0c95f24378dd46abab8ee714fccc5279
Source dataset
uspto-grants-2014_07
Patent number
US08791119B2

Reaction notes

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