Water → 69727-07-7

HRID 874148Notes

Reaction equation

HRID 874148 reaction equation
[C:1]([CH2:3][C:4]([OH:6])=O)#N.[Cl:7][C:8]1[CH:15]=[CH:14][CH:13]=[CH:12][C:9]=1C=O.[C:16]([O-])(=O)C.[NH4+:20].[OH2:21]>C1(C)C=CC=CC=1>[C:16]([C:3](=[CH:1][C:13]1[CH:14]=[CH:15][C:8]([Cl:7])=[CH:9][CH:12]=1)[C:4]([OH:6])=[O:21])#[N:20]

Participants

6

Reactant 4

HCID 962WaterHCID 69962-ChlorobenzaldehydeHCID 9740Cyanoacetic acidHCID 517165Ammonium Acetate

Product 1

HCID 22015469727-07-7

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

2 g cyanoacetic acid (1 eq., 23.5 mmol), 2.97 g chlorobenzaldehyde (0.9 eq., 21.1 mmol) and 300 mg ammonium acetate (15% (m/m) based on the acid) are heated in 30 ml toluene using a water separator with reflux. After completion of the water separation (about 3 hours), the mixture is cooled to room temperature, in the course of which the product usually precipitates in crystalline form. After filtration, the crude product is washed with sufficient water. If no product precipitates, the mixture is concentrated and the remaining solids are washed with sufficient water. The crude product is repeatedly recrystallised from a mixture of alcohol (methanol) and water. Further purification takes place by means of ion exchange (strong cation exchanger), with 50% acetonitrile being used as the solvent. The eluate is concentrated at room temperature, in the course of which the purified product precipitates in crystalline form. After filtering and drying in a vacuum, 3.35 g (78% of the theoretical yield) α-cyano-4-chloro cinnamic acid are obtained.

Workup

  1. temperaturewith reflux
  2. customAfter completion of the water separation (about 3 hours)
  3. customusually precipitates in crystalline form
  4. filtrationAfter filtration
  5. washthe crude product is washed with sufficient water
  6. customIf no product precipitates
  7. concentrationthe mixture is concentrated
  8. washthe remaining solids are washed with sufficient water
  9. customThe crude product is repeatedly recrystallised from a mixture of alcohol (methanol) and water
  10. customFurther purification
  11. concentrationThe eluate is concentrated at room temperature, in the course of which the purified product
  12. customprecipitates in crystalline form
  13. filtrationAfter filtering
  14. customdrying in a vacuum, 3.35 g (78% of the

Sources & evidence

ORD record
ord-e8cac4cfebe54078bdd6010fa871be24
Source dataset
uspto-grants-2015_03
Patent number
US08980642B2

Reaction notes

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