Ethanol → HCID 53670157, compound

HRID 1153837Notes

Reaction equation

HRID 1153837 reaction equation
[C:1]([NH:4][CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])(=[O:3])[CH3:2].ClC[C:18]1[CH:19]=[C:20]([CH:28]=[CH:29][CH:30]=1)[O:21][CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24].[Na].C(O)C>[O-]CC>[C:1]([NH:4][C:5]([C:29]1[CH:30]=[CH:18][CH:19]=[C:20]([O:21][CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH:28]=1)([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 702EthanolHCID 14041Acetamidomalonic acid diethyl esterHCID 5360545SodiumHCID 20436864HCID 20436864, compound

Product 1

HCID 53670157HCID 53670157, compound

Reagents, catalysts & solvents 1

HCID 1194401-Hydroxyethyl radicalSolvent

Procedure

Diethyl acetamidomalonate (2.60 g) and ethyl 3-(chloromethyl)phenoxyacetate (Robertson, J. Chem. Soc. 1933), 492; U.S. Pat. No. 3,933,895) (2.39 g) were dissolved in ethanolic ethoxide (prepared from sodium (230 mg) and absolute ethanol (10 ml) and the mixture refluxed for 19 hours. The cooled solution was poured into ice-water, the product was extracted into ether, and the dried extract evaporated. The residual gum was crystallised from ether/hexane to give diethyl acetamido-(3-ethoxycarbonylmethoxyphenyl)malonate as white prisms, m.p. 98.5°-101.5°. This derivative (1.90 g) was refluxed with 10% aqueous hydrochloric acid (25 ml) for 31/2 hours and the cooled solution was evaporated to dryness in vacuo. The residual white solid was dissolved in the minimum quantity of absolute ethanol and added dropwise to a stirred, cooled (-10° C.) mixture of absolute ethanol 815 ml) and thionyl chloride (1.64 g). The resulting solution was set aside at room temperature for 18 hours, refluxed for 1 hour, cooled, and poured into ice-water, adjusting the pH to 9-10 with aqueous sodium hydroxide. The mixture was extracted with ether, and the dried extract was concentrated, giving ehtyl 2-amino-3-(3-ethoxycarbonylmethoxyphenyl)propionate as a colourless oil, which was used without further purification in Examples 20 and 21.

Workup

  1. temperaturethe mixture refluxed for 19 hours
  2. extractionthe product was extracted into ether
  3. extractionthe dried extract
  4. customevaporated
  5. customThe residual gum was crystallised from ether/hexane

Sources & evidence

ORD record
ord-ecf116f52bc54ce18ebc637a90590d36
Source dataset
uspto-grants-1984_12
Patent number
US04486443

Reaction notes

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