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

HRID 2212254Notes

Reaction equation

HRID 2212254 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].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

7

Reactant 3

HCID 7410AcetophenoneHCID 7764Ethyl cyanoacetate2×HCID 517165Ammonium Acetate2×

Product 1

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

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolvent2×HCID 241BenzeneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of acetophenone (50 mmole), ethyl cyanoacetate (50 mmole), 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 mmole), acetic acid (1.14 mL), and ammonium acetate (400 mg) 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 (Na2SO4). 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/petroleum ether, affording an oil that solidified on standing at room temperature.

Workup

  1. temperaturewas heated
  2. temperatureto reflux in a Dean-Stark apparatus
  3. waitAfter an additional 10 hours
  4. washwashed with water (240 mL), brine (40 mL)
  5. dry with materialdried (Na2SO4)
  6. filtrationAfter filtering
  7. concentrationthe extract was concentrated in vacuo
  8. additionthe desired product, as a mixture of E- and Z-isomers
  9. customwas isolated by column chromatography on silica gel
  10. washeluting with 5% ethyl acetate/petroleum ether
  11. customaffording an oil that
  12. customon standing at room temperature

Sources & evidence

ORD record
ord-5cbf05ded4a148d79f09583f84c8d4de
Source dataset
uspto-grants-2006_09
Patent number
US07101905B2

Reaction notes

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