Acetophenone → Ethyl 2-cyano-3-phenyl-2-butenoate

HRID 270163Notes

Reaction equation

HRID 270163 reaction equation
[C:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)(=O)[CH3:2].[C:10]([CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])#[N:11].CC(OCC1C2C(=CC=CC=2)C(COC(C)=O)=C2C=1C=CC=C2)=O.C([O-])(=O)C.[NH4+]>C(OCC)(=O)C.C(O)(=O)C.C1C=CC=CC=1>[CH2:16]([O:15][C:13](=[O:14])[C:12]([C:10]#[N:11])=[C:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)[CH3:2])[CH3:17]

Participants

8

Reactant 4

HCID 7410AcetophenoneHCID 7764Ethyl cyanoacetate2×HCID 517165Ammonium Acetate2×HCID 613145Acetic acid 10-acetoxymethyl-anthracen-9-ylmethyl ester

Product 1

HCID 29024Ethyl 2-cyano-3-phenyl-2-butenoate

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 241BenzeneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of acetophenone (50 mmol), ethyl cyanoacetate (50 mmol), acetic; acid (1.14 mL), ammonium acetate (400 mg), and benzene (50 mL) was heated to reflux in a Dean-Stark apparatus. After approximately 10 hours, additional ethyl cyanoacetate (50 mmol), acetic acid (1.14 mL), and ammonium acetate (400 mL) are added. After an additional 10 hours, the reaction was cooled to room temperature, diluted with ethyl acetate (30 mL), washed with water (240 mL), brine (40 mL), and dried (Na2S04). After filtering, the extract was concentrated in vacuo and the desired product, as a mixture of E and Z-isomers, was isolated by column chromatography on silica gel, eluting with 5% ethyl acetate in petroleum ether, affording an oil that solidified on standing at room temperature.

Workup

  1. temperatureto reflux in a Dean-Stark apparatus
  2. waitAfter an additional 10 hours
  3. washwashed with water (240 mL), brine (40 mL)
  4. customdried (Na2S04)
  5. filtrationAfter filtering
  6. concentrationthe extract was concentrated in vacuo
  7. additionthe desired product, as a mixture of E and Z-isomers
  8. customwas isolated by column chromatography on silica gel
  9. washeluting with 5% ethyl acetate in petroleum ether
  10. customaffording an oil that
  11. customon standing at room temperature

Sources & evidence

ORD record
ord-2cbe06d157694f0eb7719a4485f3438d
Source dataset
uspto-grants-2008_11
Patent number
US07449490B2

Reaction notes

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