Acetic Acid → Ethyl 3-(4-Fluorophenyl)-3-Oxopropanoate

HRID 1609570Notes

Reaction equation

HRID 1609570 reaction equation
[H-].[Na+].[C:3](=[O:10])([O:7][CH2:8][CH3:9])OCC.[CH3:11][C:12]([C:14]1[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=1)=[O:13].C(O)(=O)C>C(OCC)C.O>[F:20][C:17]1[CH:18]=[CH:19][C:14]([C:12]([CH2:11][C:3]([O:7][CH2:8][CH3:9])=[O:10])=[O:13])=[CH:15][CH:16]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 7766Diethyl CarbonateHCID 98284'-FluoroacetophenoneHCID 24758Sodium hydride

Product 1

HCID 2758844Ethyl 3-(4-Fluorophenyl)-3-Oxopropanoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent3×

Conditions

Temperature
5 °C

Procedure

21.7 g (0.72 mol) of sodium hydride (80% strength, 20% mineral oil) are weighed into a liter of diethyl ether p.a. and 85.5 g (127 ml, 0.72 mol) of diethyl carbonate (VK 22-010) are subsequently added. A solution of 100 g (0.72 mol) of 4-fluoroacetophenone in 300 ml of diethyl ether are added dropwise to this solution at boiling heat over a period of 4 hours (vigorous, mechanical stirrer necessary; a viscous paste is formed). The mixture is then heated to reflux for a further hour, then cooled to about 5° C. and a solution of 50 ml of acetic acid and 100 ml of Et2O is next added dropwise under N2 at this temperature. About 500 ml of H2O are subsequently added dropwise and the organic phase is separated off. The aqueous phase is extracted once again using Et2O (2×400 ml), and the combined ethereal phases are washed with NaHCO3 solution, dried over MgSO4 and concentrated. The residue is distilled over a short Vigreux column.

Workup

  1. temperatureat boiling heat over a period of 4 hours (vigorous, mechanical stirrer necessary
  2. customa viscous paste is formed)
  3. temperatureThe mixture is then heated
  4. temperatureto reflux for a further hour
  5. customthe organic phase is separated off
  6. extractionThe aqueous phase is extracted once again using Et2O (2×400 ml)
  7. washthe combined ethereal phases are washed with NaHCO3 solution
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated
  10. distillationThe residue is distilled over a short Vigreux column

Sources & evidence

ORD record
ord-af6b680e991c4fd6823b939b4577a77e
Source dataset
uspto-grants-1995_03
Patent number
US05401746

Reaction notes

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