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

HRID 1493843Notes

Reaction equation

HRID 1493843 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-fe786c13c5b743e896422e50daf66a00
Source dataset
uspto-grants-1991_06
Patent number
US05025000

Reaction notes

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