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

HRID 890864Notes

Reaction equation

HRID 890864 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[C:2]([O:4]C)=O.[Cl:9][C:10]1[CH:15]=[CH:14][C:13]([C:16](=[O:18])[CH3:17])=[CH:12][CH:11]=1.Cl>CO.C[O-].[Na+]>[CH3:8][O:7][C:1](=[O:6])[C:2](=[O:4])[CH2:17][C:16]([C:13]1[CH:14]=[CH:15][C:10]([Cl:9])=[CH:11][CH:12]=1)=[O:18]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 7467P-ChloroacetophenoneHCID 11120Dimethyl oxalate

Product 1

HCID 308124methyl 4-(4-chlorophenyl)-2,4-dioxobutanoate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 10942334Sodium MethoxideSolvent

Procedure

Dimethyl oxalate (15.27 g, 0.129 mol) and 4′-chloroacetophenone (20.0 g, 0.129 mol) were diluted with methanol (300 mL) and sodium methoxide (25 wt % in methanol, 70 mL) was added in one portion. The reaction was stirred at room temperature for 16 hours (the reaction became an insoluble mass during this time). The solid was mechanically broken up, hydrochloric acid (conc. 70 mL) was added, 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). Upon drying, methyl-4-[4-(chloro)phenyl]-2,4-dioxobutanoate was obtained (16.94 g, 54.4%) as the enol: mp 108.5–110.5° C. 1H NMR (CDCl3/300 MHz) δ 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. additionwas added in one portion
  2. stirringthe white suspension was stirred vigorously at room temperature for 1 hour
  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. customUpon drying

Sources & evidence

ORD record
ord-f8c20c65f765427c8c93e73ab2876700
Source dataset
uspto-grants-2006_02
Patent number
US06998415B2

Reaction notes

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