Ethanol → Diethyl 2-(2,4-dichlorophenyl)malonate

HRID 846364Notes

Reaction equation

HRID 846364 reaction equation
[Na].C(O)C.[Cl:5][C:6]1[CH:11]=[C:10]([Cl:12])[CH:9]=[CH:8][C:7]=1[CH2:13][C:14]([O:16][CH2:17][CH3:18])=[O:15].[C:19](=O)([O:23]CC)[O:20][CH2:21][CH3:22]>>[CH3:18][CH2:17][O:16][C:14]([CH:13]([C:19]([O:20][CH2:21][CH3:22])=[O:23])[C:7]1[CH:8]=[CH:9][C:10]([Cl:12])=[CH:11][C:6]=1[Cl:5])=[O:15]

Participants

5

Reactant 4

HCID 702Ethanol2×HCID 7766Diethyl CarbonateHCID 234291Ethyl (2,4-dichlorophenyl)acetateHCID 5360545Sodium2×

Product 1

HCID 2736112Diethyl 2-(2,4-dichlorophenyl)malonateYield 85%

Procedure

Sodium (1.86 g, 0.08M) was added in portions to absolute ethanol (150 ml) with stirring. After all the sodium had dissolved a solution of ethyl 2,4-dichlorophenylacetate (20 g) in diethyl carbonate (50 ml) was added dropwise. The reaction mixture was heated until EtOH distilled over. The rate of addition was controlled such that it equalled the rate of distillation. After the completion of addition the reaction mixture was heated and distilled for further 4 hours. The cooled reaction mixture was partitioned between water (300 ml) and EtOAc (300 ml) and the organic layer dried and evaporated in vacuo to give a yellow oil (21 g, 85%).

Workup

  1. additionwas added dropwise
  2. distillationdistilled over
  3. additionThe rate of addition
  4. distillationthe rate of distillation
  5. additionAfter the completion of addition the reaction mixture
  6. temperaturewas heated
  7. distillationdistilled for further 4 hours
  8. customThe cooled reaction mixture
  9. customwas partitioned between water (300 ml) and EtOAc (300 ml)
  10. customthe organic layer dried
  11. customevaporated in vacuo

Sources & evidence

ORD record
ord-d9332eb39a6e46da8e936cef12f197f2
Source dataset
uspto-grants-1992_08
Patent number
US05136080

Reaction notes

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