Sulfuric Acid → Diethyl (2-bromo-4,5-difluorobenzoyl)malonate

HRID 1788657Notes

Reaction equation

HRID 1788657 reaction equation
[Mg].[C:2]([O:10][CH2:11][CH3:12])(=[O:9])[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].[Br:13][C:14]1[CH:22]=[C:21]([F:23])[C:20]([F:24])=[CH:19][C:15]=1[C:16](Cl)=[O:17].S(=O)(=O)(O)O>C(O)C.CCOCC.C(Cl)(Cl)(Cl)Cl>[Br:13][C:14]1[CH:22]=[C:21]([F:23])[C:20]([F:24])=[CH:19][C:15]=1[C:16]([CH:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])[C:2]([O:10][CH2:11][CH3:12])=[O:9])=[O:17]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 7761Diethyl MalonateHCID 27832942-Bromo-4,5-difluorobenzoyl chlorideHCID 5462224Magnesium

Product 1

HCID 14347789Diethyl (2-bromo-4,5-difluorobenzoyl)malonateYield 108.2%

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent2×HCID 3283Diethyl EtherSolvent2×HCID 5943Carbon TetrachlorideSolvent

Procedure

Magnesium ribbon (7.3 g) is suspended in absolute ethanol (15 ml), and thereto is added carbon tetrachloride (1.5 ml), and thereto is added dropwise a mixture of diethyl malonate (48 g), absolute ethanol (30 ml) and anhydrous ether (120 ml) over a period of one hour. After the addition, the mixture is refluxed for 2 hours. After cooling till room temperature, a solution of 2-bromo-4,5-difluorobenzoyl chloride (92 g) in anhydrous ether (50 ml) is added dropwise to the mixture. After the addition, the mixture is allowed to stand overnight at room temperature. A mixture of ice-water (120 ml) and conc. sulfuric acid (8 ml) is added dropwise to the reaction mixture under ice-cooling. After the addition, the mixture is extracted with ether. The ether layer is washed with saturated aqueous sodium chloride solution and dried over magnesium sulfate. The solvent is distilled off under reduced pressure to give diethyl (2-bromo-4,5-difluorobenzoyl)malonate (123 g).

Workup

  1. additionis added dropwise
  2. additionAfter the addition
  3. temperaturethe mixture is refluxed for 2 hours
  4. additionAfter the addition
  5. additionis added dropwise to the reaction mixture under ice-
  6. temperaturecooling
  7. additionAfter the addition
  8. extractionthe mixture is extracted with ether
  9. washThe ether layer is washed with saturated aqueous sodium chloride solution
  10. dry with materialdried over magnesium sulfate
  11. distillationThe solvent is distilled off under reduced pressure

Sources & evidence

ORD record
ord-575364d959734897b000c05ed2143923
Source dataset
uspto-grants-1987_08
Patent number
US04684648

Reaction notes

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