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

HRID 1788663Notes

Reaction equation

HRID 1788663 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 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 to the mixture under ice-cooling. After the addition, the mixture is stirred at room temperature for 3 hours and 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. After the addition, the mixture is stirred at room temperature for 30 minutes. The ether layer is separated, and the remaining solution is extracted with ether. The ether layers are combined and 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-tetrafluorobenzoyl)malonate (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. additionAfter the addition
  10. stirringthe mixture is stirred at room temperature for 30 minutes
  11. customThe ether layer is separated
  12. extractionthe remaining solution is extracted with ether
  13. washwashed 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-a6b3182d98c34f5c86077f7c0968b460
Source dataset
uspto-grants-1987_08
Patent number
US04684648

Reaction notes

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