Acetic Acid → Ethyl 2-cyano-3-phenyl-2-butenoate

HRID 1771929Notes

Reaction equation

HRID 1771929 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(O)(=O)C>O.C1(C)C=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 4

HCID 176Acetic AcidHCID 7410AcetophenoneHCID 7764Ethyl cyanoacetateHCID 517165Ammonium Acetate

Product 1

HCID 29024Ethyl 2-cyano-3-phenyl-2-butenoateYield 110.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A stirred mixture of acetophenone (VIII) (180 g, 1.5 mol), ethyl cyanoacetate (170 g, 1.3 mol), ammonium acetate (23.1 g), acetic acid (72 g) and toluene (300 ml) was heated under reflux for 18 hours while water was removed from the reaction by azeotropic distillation. The mixture was allowed to cool to ambient temperature, toluene (100 ml) was added, then the mixture was washed with water (3×100 ml). The combined aqueous washings were shaken with toluene (50 ml), then the combined toluene solutions were dried over magnesium sulphate, filtered and the solvent was removed in vacuo. The residual oil was distilled under reduced pressure to give 2-cyano-3-phenyl-but-2-enoic acid ethyl ester as an oil (309 g) which was used without further purification.

Workup

  1. temperaturewas heated
  2. customwas removed from the reaction by azeotropic distillation
  3. additiontoluene (100 ml) was added
  4. washthe mixture was washed with water (3×100 ml)
  5. dry with materialthe combined toluene solutions were dried over magnesium sulphate
  6. filtrationfiltered
  7. customthe solvent was removed in vacuo
  8. distillationThe residual oil was distilled under reduced pressure

Sources & evidence

ORD record
ord-3ca18dbde67c4f28aa25f7b4bfe3b139
Source dataset
uspto-grants-2016_02
Patent number
US09249155B2

Reaction notes

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