Methyl cyanoacetate → Methyl 3-amino-3-phenylprop-2-enoate

HRID 1978861Notes

Reaction equation

HRID 1978861 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Mg].[C:9]([CH2:11][C:12]([O:14][CH3:15])=[O:13])#[N:10].[Cl-].[NH4+]>CCOCC>[NH2:10][C:9]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[CH:11][C:12]([O:14][CH3:15])=[O:13]

Participants

6

Reactant 4

HCID 7747Methyl cyanoacetateHCID 7961BromobenzeneHCID 25517Ammonium ChlorideHCID 5462224Magnesium

Product 1

HCID 66920106Methyl 3-amino-3-phenylprop-2-enoateYield 73.4%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

47 g of bromobenzene in 90 ml of ether were added dropwise to 7.2 g of magnesium in 20 ml of ether under reflux, and the stirred mixture was refluxed for 1 hour. Thereafter, 9.9 g of methyl cyanoacetate were added dropwise while cooling with ice, and stirring was carried out for 1 hour at room temperature, for 5 hours under reflux and again for 15 hours at room temperature. 300 ml of ammonium chloride were carefully added to the reaction mixture and the aqueous phase was extracted twice with ether and the combined organic phases were washed three times with water, dried over sodium sulfate and evaporated down. The residue was distilled under greatly reduced pressure. 13 g of methyl β-amino-cinnamate were obtained (110-112° C., 10.15 mbar).

Workup

  1. temperatureunder reflux
  2. temperaturethe stirred mixture was refluxed for 1 hour
  3. temperaturewhile cooling with ice
  4. extractionthe aqueous phase was extracted twice with ether
  5. washthe combined organic phases were washed three times with water
  6. dry with materialdried over sodium sulfate
  7. customevaporated down
  8. distillationThe residue was distilled under greatly reduced pressure

Sources & evidence

ORD record
ord-ec469162d2da4e20908f7efe0dc16a10
Source dataset
uspto-grants-2001_05
Patent number
US06239074B1

Reaction notes

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