Diethyl Carbonate → Ethyl 3-(4-Fluorophenyl)-3-Oxopropanoate

HRID 893428Notes

Reaction equation

HRID 893428 reaction equation
[H-].[Na+].[C:3](=[O:10])([O:7][CH2:8][CH3:9])OCC.[F:11][C:12]1[CH:17]=[CH:16][C:15]([C:18](=[O:20])[CH3:19])=[CH:14][CH:13]=1>C(O)C>[F:11][C:12]1[CH:17]=[CH:16][C:15]([C:18](=[O:20])[CH2:19][C:3]([O:7][CH2:8][CH3:9])=[O:10])=[CH:14][CH:13]=1

Participants

5

Reactant 3

HCID 7766Diethyl CarbonateHCID 98284'-FluoroacetophenoneHCID 24758Sodium hydride

Product 1

HCID 2758844Ethyl 3-(4-Fluorophenyl)-3-OxopropanoateYield 78.4%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a suspension of sodium hydride (29.5 g of 60% oil dispersion, washed free of oil with hexane) in diethyl carbonate (88 mL, 0.726 mol) at room temperature under argon was added dropwise over 30 minutes p-fluoroacetophenone (50.0 g, 0.362 mol). Ethanol (0.1 mL) was added during the addition to initiate the reaction. After 2/3 of the ketone had been added, white solid had separated and Et2O (600 mL) was added to facilitate stirring. When the addition was complete the mixture was refluxed for 3 hours. The mixture was then placed in an ice bath, and the reaction was quenched by the dropwise addition of water (100 mL) and 5% KHSO4 solution (100 mL). The mixture was acidified with 10% H2SO4, the organic phase separated and washed with saturated NaHCO3 and saturated NaCl solutions, dried (MgSO4) and evaporated. The residue was distilled in vacuo to give title compound (59.66 g, 78%) as a colorless liquid, bp 115°-118° C. (1 mmHg).

Workup

  1. customthe reaction
  2. customwhite solid had separated
  3. additionEt2O (600 mL) was added
  4. additionWhen the addition
  5. temperaturewas refluxed for 3 hours
  6. customThe mixture was then placed in an ice bath
  7. customthe reaction was quenched by the dropwise addition of water (100 mL) and 5% KHSO4 solution (100 mL)
  8. customthe organic phase separated
  9. washwashed with saturated NaHCO3 and saturated NaCl solutions
  10. dry with materialdried (MgSO4)
  11. customevaporated
  12. distillationThe residue was distilled in vacuo

Sources & evidence

ORD record
ord-209097d361e44240943ac32e3a5a6d50
Source dataset
uspto-grants-1992_06
Patent number
US05124453

Reaction notes

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