Acetic Acid → 2-Cyano-3-phenylprop-2-enoic acid

HRID 358120Notes

Reaction equation

HRID 358120 reaction equation
[CH:1](=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:9]([CH2:11][C:12]([OH:14])=[O:13])#[N:10].C(O)(=O)C.C([O-])(=O)C.[NH4+]>C(O)C>[C:9]([C:11](=[CH:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:12]([OH:14])=[O:13])#[N:10]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 240BenzaldehydeHCID 9740Cyanoacetic acidHCID 517165Ammonium Acetate

Product 1

HCID 705342-Cyano-3-phenylprop-2-enoic acidYield 81.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Benzaldehyde (200 g), cyanoacetic acid (176 g), acetic acid (30 ml) and ammonium acetate (14.5 g) were refluxed for 4 hours in ethyl alcohol (800 ml) with heating. After the reaction, the mixture was concentrated to 400 ml by removing ethyl alcohol under a reduced pressure, followed by pouring into 1 liter of ice water to separate crystals. The resulting crystals were recrystallized from 250 ml of acetonitrile to obtain 265 g of 2-cyano-3-phenylacrylic acid which melted at 184° to 188° C. The resulting compound (150 g) and thionyl chloride (176 g) were dissolved in acetonitrile (100 ml) with heating for 1 hour. After the reaction, the acetonitrile and the thionyl chloride were distilled off under a reduced pressure, and the resulting solid was added to a solution consisting of hydroxyethyl methacrylate (124 g), pyridine (75 g) and acetonitrile (1 l). The reaction was carried out for 2 hours while keeping the reaction temperature below 40° C. After the reaction, the reaction solution was poured into ice water to separate crystals, and the resulting crystals were recrystallized from ethyl alcohol (1 l) to obtain 205 g of the desired compound which melted at 68° to 70° C.

Workup

  1. temperaturewith heating
  2. customAfter the reaction
  3. concentrationthe mixture was concentrated to 400 ml
  4. customby removing ethyl alcohol under a reduced pressure
  5. additionby pouring into 1 liter of ice water
  6. customto separate crystals
  7. customThe resulting crystals were recrystallized from 250 ml of acetonitrile

Sources & evidence

ORD record
ord-73ac97baa1e04a57ac1c6ae95b9e7c92
Source dataset
uspto-grants-1984_08
Patent number
US04464462

Reaction notes

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