Hydrochloric Acid → methyl 4-(4-fluorophenyl)-2,4-dioxobutanoate

HRID 2084707Notes

Reaction equation

HRID 2084707 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[C:2]([O:4]C)=O.[F:9][C:10]1[CH:15]=[CH:14][C:13]([C:16](=[O:18])[CH3:17])=[CH:12][CH:11]=1.C[O-].[Na+].Cl>CO>[F:9][C:10]1[CH:15]=[CH:14][C:13]([C:16](=[O:18])[CH2:17][C:2](=[O:4])[C:1]([O:7][CH3:8])=[O:6])=[CH:12][CH:11]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 98284'-FluoroacetophenoneHCID 11120Dimethyl oxalateHCID 10942334Sodium Methoxide

Product 1

HCID 4552592methyl 4-(4-fluorophenyl)-2,4-dioxobutanoate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Dimethyl oxalate (18.80 g, 0.159 mol) and 4′-fluoroacetophenone (20.0 g, 0.145 mol) were charged to a 1000 mL round-bottom flask and diluted with methanol (400 mL). The reaction flask was placed in a sonication bath (Bransonic 1200), and sodium methoxide (25% in methanol, 70 mL) was added over 25 minutes. The reaction was sonicated at 45° C. for 16 hours. The reaction became an insoluble mass during this time. The solid was mechanically broken up, then poured into a hydrochloric acid solution (1N, 500 mL). A magnetic stirrer was added, and the white suspension was stirred vigorously at room temperature for 60 minutes. The suspension was cooled to 0° C. and held for 30 minutes. The solid was filtered, and the filter cake was then washed with cold water (100 mL). Upon drying, methyl 4-[4-fluorophenyl]-2,4-diketobutanoate was obtained (22.91 g, 70.6%) as the enol: 1H NMR (CDCl3/300 MHz) 8.03 (ddd, J=8.86 Hz, J=8.66 Hz, J=5.03 Hz, 2H), 7.19 (dd, J=8.86 Hz, J=8.66 Hz, 2H), 7.04 (s, 1H), 3.95 (s, 3H). 19F NMR (CDCl3/282.2 MHz) −103.9(m).

Workup

  1. customThe reaction flask was placed in a sonication bath
  2. customThe reaction was sonicated at 45° C. for 16 hours
  3. additionA magnetic stirrer was added
  4. temperatureThe suspension was cooled to 0° C.
  5. waitheld for 30 minutes
  6. filtrationThe solid was filtered
  7. washthe filter cake was then washed with cold water (100 mL)
  8. customUpon drying

Sources & evidence

ORD record
ord-fde2eb8da53843f19a00f58d68c5d3d5
Source dataset
uspto-grants-2004_04
Patent number
US06716991B1

Reaction notes

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