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

HRID 270170

Reaktionsgleichung

Reaktionsgleichung von HRID 270170
[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]

Komponenten

7

Edukt 3

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 176Acetic AcidLösungsmittel2×HCID 241BenzeneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

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%.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-fc75c8a19bce49d2825fab20f849b1a6
Quelldatensatz
uspto-grants-2008_11
Patentnummer
US07449490B2

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