2,2-Dimethyl-1,3-dioxane-4,6-dione → Ethyl 4-(4-fluorophenyl)-3-oxobutanoate

HRID 1472610Notes

Reaction equation

HRID 1472610 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9](Cl)=[O:10])=[CH:4][CH:3]=1.[CH3:12][C:13]1(C)[O:18]C(=O)[CH2:16][C:15](=O)[O:14]1.CCN(C(C)C)C(C)C>C(Cl)Cl>[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9](=[O:10])[CH2:12][C:13]([O:14][CH2:15][CH3:16])=[O:18])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 162492,2-Dimethyl-1,3-dioxane-4,6-dioneHCID 81531DiisopropylethylamineHCID 37449884-Fluorophenylacetyl chloride

Product 1

HCID 10585213Ethyl 4-(4-fluorophenyl)-3-oxobutanoateYield 97.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A mixture of 4-fluorophenylacetyl chloride (4.91 g, 24.3 mmol), 2,2-dimethyl-1,3-dioxane-4,6-dione (3.50 g, 24.3 mmol) and DIEA (5.84 g, 49.8 mmol) in DCM (30 mL) was stirred for 1 h at 0° C., then warmed to RT for 2 h. The solution was diluted with DCM, washed with 0.1 N HCl and brine, dried over Na2SO4 and evaporated to dryness. The resulting orange solid was suspended in EtOH (100 mL) and refluxed for 2 hours. The solution was evaporated and the resulting orange oil was left in the freezer overnight to give a yellow solid. The crude solid was recrystallized from EtOH to afford ethyl 4-(4-fluorophenyl)-3-oxobutanoate (5.3 g, 86.8% yield).

Workup

  1. temperaturewarmed to RT for 2 h
  2. washwashed with 0.1 N HCl and brine
  3. dry with materialdried over Na2SO4
  4. customevaporated to dryness
  5. temperaturerefluxed for 2 hours
  6. customThe solution was evaporated
  7. waitthe resulting orange oil was left in the freezer overnight
  8. customto give a yellow solid
  9. customThe crude solid was recrystallized from EtOH

Sources & evidence

ORD record
ord-41bc4e70ce71455e80f0c5299a655339
Source dataset
uspto-grants-2015_04
Patent number
US09012635B2

Reaction notes

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