Sulfuric Acid → 1,3-Diethyl 2-(2,3,4,5-tetrafluorobenzoyl)propanedioate

HRID 845023Notes

Reaction equation

HRID 845023 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].[F:13][C:14]1[C:22]([F:23])=[C:21]([F:24])[C:20]([F:25])=[CH:19][C:15]=1[C:16](Cl)=[O:17].S(=O)(=O)(O)O>C(O)C.CCOCC.C(Cl)(Cl)(Cl)Cl>[F:13][C:14]1[C:22]([F:23])=[C:21]([F:24])[C:20]([F:25])=[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 27336892,3,4,5-Tetrafluorobenzoyl chlorideHCID 5462224Magnesium

Product 1

HCID 135649731,3-Diethyl 2-(2,3,4,5-tetrafluorobenzoyl)propanedioate

Reagents, catalysts & solvents 3

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

Procedure

Magnesium ribbon (0.11 g) is suspended in absolute ethanol (0.5 ml), and thereto is added carbon tetrachloride (0.05 ml). After 10 minutes, to the mixture is added dropwise a mixture of diethyl malonate (1.5 ml), absolute ethanol (0.9 ml) and anhydrous ether (3.8 ml) at a room temperature. After the addition, the mixture is refluxed for 3 hours. Thereafter, a solution of 2,3,4,5-tetrafluorobenzoyl chloride (2.0 g) in anhydrous ether (0.9 ml) is added dropwise under ice-cooling. After the addition, the mixture is stirred at room temperature for 3 hours, and then allowed to stand overnight. A mixture of ice-water (4 ml) and conc. sulfuric acid (0.24 ml) is added dropwise to the reaction mixture under ice-cooling, and the mixture is stirred at room temperature for 30 minutes. The ether layer is separated, and the remaining reaction mixture is extracted with ether. The ether layers are combined, and are washed with saturated aqueous sodium chloride solution and dried over magnesium sulfate. The solvent is distilled off under reduced pressure to give diethyl 2,3,4,5-tetrafluorobenzoylmalonate (3.0 g).

Workup

  1. additionto the mixture is added dropwise
  2. additionAfter the addition
  3. temperaturethe mixture is refluxed for 3 hours
  4. temperaturecooling
  5. additionAfter the addition
  6. waitto stand overnight
  7. additionis added dropwise to the reaction mixture under ice-
  8. temperaturecooling
  9. stirringthe mixture is stirred at room temperature for 30 minutes
  10. customThe ether layer is separated
  11. customthe remaining reaction mixture
  12. extractionis extracted with ether
  13. washare washed with saturated aqueous sodium chloride solution
  14. dry with materialdried over magnesium sulfate
  15. distillationThe solvent is distilled off under reduced pressure

Sources & evidence

ORD record
ord-cb46ea38917f496286967cc5859817e7
Source dataset
uspto-grants-1988_07
Patent number
US04755513

Reaction notes

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