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

HRID 1274280Notes

Reaction equation

HRID 1274280 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[C:2]([O:4]C)=O.C[O-].[Na+].[Cl:12][C:13]1[CH:18]=[CH:17][C:16]([C:19](=[O:21])[CH3:20])=[CH:15][CH:14]=1.Cl>C(OCC)C.CO.C(OCC)(=O)C>[CH3:8][O:7][C:1](=[O:6])[C:2](=[O:4])[CH2:20][C:19]([C:16]1[CH:17]=[CH:18][C:13]([Cl:12])=[CH:14][CH:15]=1)=[O:21]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 7467P-ChloroacetophenoneHCID 11120Dimethyl oxalateHCID 10942334Sodium Methoxide

Product 1

HCID 308124methyl 4-(4-chlorophenyl)-2,4-dioxobutanoateYield 95%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 3283Diethyl EtherSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Dimethyl oxalate (23.6 g, 200 mmol) was placed in a 500 mL three-necked round bottom flask, and dissolved in diethyl ether (200 mL). To the stirred solution was added 25% sodium methoxide in methanol (48 mL, 210 mmol: via an addition funnel over a 2 minute period. Next, 4'-chloroacetophenone (25.94 g, 200 mmol) was dissolved in diethyl ether (50 mL), and added to the reaction dropwise over 3 minutes. After stirring overnight (18 hours), 1N HCl (400 mL) and ethyl acetate (750 mL) were added. The organic layer was collected, washed with brine (350 mL), dried over MgSO4, filtered, and concentrated in vacuo to give 45.7 g of a yellow solid. The solid was recrystallized from ethyl acetate and iso-octane to give 23 g (48%) of the dione: mp 108.5-110.5° C.

Workup

  1. additionadded to the reaction dropwise over 3 minutes
  2. additionwere added
  3. customThe organic layer was collected
  4. washwashed with brine (350 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-a8d5b92b886f4db1acc03963010c4ed9
Source dataset
uspto-grants-2000_12
Patent number
US06156781

Reaction notes

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