Ethyl cyanoacetate → 3-(3-Chlorophenyl)-2-cyano-but-2-enoic acid ethyl ester

HRID 270170

Reaction equation

HRID 270170 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:8](=O)[CH3:9])[CH:5]=[CH:6][CH:7]=1.[C:11]([CH2:13][C:14]([O:16][CH2:17][CH3:18])=[O:15])#[N:12].C([O-])(=O)C.[NH4+]>C(OCC)(=O)C.C(O)(=O)C.C1C=CC=CC=1>[CH2:17]([O:16][C:14](=[O:15])[C:13]([C:11]#[N:12])=[C:8]([C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([Cl:1])[CH:3]=1)[CH3:9])[CH3:18]

Participants

7

Reactant 3

HCID 7764Ethyl cyanoacetate2×HCID 149331-(3-Chlorophenyl)ethanoneHCID 517165Ammonium Acetate

Product 1

HCID 670739253-(3-Chlorophenyl)-2-cyano-but-2-enoic acid ethyl esterYield 60%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolvent2×HCID 241BenzeneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 3′-chloroacetophenone (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 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 1:1 mixture of E and Z-isomers, was isolated by column chromatography on silica gel, eluting with 5% ethyl acetate in petroleum ether. The purified oil solidified on standing at room temperature Yield: 60%.

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 1:1 mixture of E and Z-isomers
  9. customwas isolated by column chromatography on silica gel
  10. washeluting with 5% ethyl acetate in petroleum ether
  11. customon standing at room temperature

Sources & evidence

ORD record
ord-fc75c8a19bce49d2825fab20f849b1a6
Source dataset
uspto-grants-2008_11
Patent number
US07449490B2

Linked notes

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