P-Chloroacetophenone → Methyl 3-oxo-4-(4-chlorophenyl)butanoate

HRID 263644Notes

Reaction equation

HRID 263644 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[C:2](OC)=O.[Cl:9][C:10]1[CH:15]=[CH:14][C:13]([C:16](=O)[CH3:17])=[CH:12][CH:11]=1.C[O-].[Na+].[Na].C([O-])(=[O:27])CCC>CO>[Cl:9][C:10]1[CH:15]=[CH:14][C:13]([CH2:16][C:17](=[O:27])[CH2:2][C:1]([O:7][CH3:8])=[O:6])=[CH:12][CH:11]=1

Participants

7

Reactant 5

HCID 7467P-ChloroacetophenoneHCID 11120Dimethyl oxalateHCID 104775ButyrateHCID 5360545SodiumHCID 10942334Sodium Methoxide

Product 1

HCID 22246215Methyl 3-oxo-4-(4-chlorophenyl)butanoate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Dimethyl oxalate (15.27 g, 0,129 mol), and 4'-chloroacetophenone (20.0 g, 0.129 mol) were added to methanol (300 mL). Sodium methoxide (25 wt. % in methanol, 70 mL) was added dropwise over about 0.5 hour. The reaction was stirred at room temperature for 16 hours, whereupon the sodium salt of the butanoate precipitated from solution. The mixture was treated with 70 mL of conc. HCl and the white suspension was stirred vigorously at room temperature for 1 hour. The suspension was cooled to 0° C. and held for 0.5 hour. The solid was filtered, and the filter cake was washed with cold water (100 mL). After drying in vacuo, methyl 4-[4-(chloro)phenyl]-3-ketobutyrate was obtained (16.94 g, 54.4%) as the enol: 1H NMR (CDCl3 /300 MHz) 8 7.94 (d, J=8.66 Hz, 2H), 7.48 (d, J=8.66 Hz, 2H), 7.04 (s, 1H), 3.95 (s, 3H), 3.48 (s, 1H).

Workup

  1. customprecipitated from solution
  2. additionThe mixture was treated with 70 mL of conc. HCl
  3. temperatureThe suspension was cooled to 0° C.
  4. waitheld for 0.5 hour
  5. filtrationThe solid was filtered
  6. washthe filter cake was washed with cold water (100 mL)
  7. customAfter drying in vacuo

Sources & evidence

ORD record
ord-fc6349c0750e4c6fae39c6f3f62f6318
Source dataset
uspto-grants-1997_07
Patent number
US05643933

Reaction notes

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