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

HRID 1941690Notes

Reaction equation

HRID 1941690 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[C:2]([O:4]C)=O.C[O-].[Na+].CO.[Cl:14][C:15]1[CH:20]=[CH:19][C:18]([C:21](=[O:23])[CH3:22])=[CH:17][CH:16]=1.Cl>C(OCC)C.C(OCC)(=O)C>[CH3:8][O:7][C:1](=[O:6])[C:2](=[O:4])[CH2:22][C:21]([C:18]1[CH:19]=[CH:20][C:15]([Cl:14])=[CH:16][CH:17]=1)=[O:23]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 887MethanolHCID 7467P-ChloroacetophenoneHCID 11120Dimethyl oxalateHCID 10942334Sodium Methoxide

Product 1

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

Reagents, catalysts & solvents 2

HCID 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-8728c19b691849d285beb6d3b7d1c141
Source dataset
uspto-grants-2013_03
Patent number
USRE044048E1

Reaction notes

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