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

HRID 745477Notes

Reaction equation

HRID 745477 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].C(=O)=O.CC(C)=O.[F:20][C:21]1[C:29]([F:30])=[C:28]([F:31])[C:27]([F:32])=[CH:26][C:22]=1[C:23](Cl)=[O:24].S(=O)(=O)(O)O>C(O)C.C1(C)C=CC=CC=1.C(Cl)(Cl)(Cl)Cl>[F:20][C:21]1[C:29]([F:30])=[C:28]([F:31])[C:27]([F:32])=[CH:26][C:22]=1[C:23]([CH:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])[C:2]([O:10][CH2:11][CH3:12])=[O:9])=[O:24]

Participants

9

Reactant 5

HCID 1118Sulfuric AcidHCID 7761Diethyl MalonateHCID 27336892,3,4,5-Tetrafluorobenzoyl chlorideHCID 5462224MagnesiumHCID 18522661Acetone cardice

Product 1

HCID 135649731,3-Diethyl 2-(2,3,4,5-tetrafluorobenzoyl)propanedioateYield 99.7%

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent2×HCID 1140TolueneSolvent2×HCID 5943Carbon TetrachlorideSolvent

Procedure

24.3 g of magnesium turnings are suspended in 50 ml of anhydrous ethanol. 5 ml of carbon tetrachloride are added and, when the reaction has started, a mixture of 160 g of diethyl malonate, 100 ml of absolute ethanol and 400 ml of anhydrous toluene are added dropwise at 50°-60° C. The mixture is then heated at 50°-60° C. for a further 1 hour, cooled with dry ice/acetone to -5° C. to -10° C. and a solution of 212.5 g of 2,3,4,5-tetrafluorobenzoyl chloride in 80 ml of absolute toluene is slowly added dropwise at this temperature. The mixture is stirred at 0° to -5° C. for 1 hour, allowed to reach room temperature overnight, and is then run into a mixture of 400 ml of ice-water and 25 ml of concentrated sulphuric acid while cooling in ice. The phases are separated and two further extractions with toluene are carried out. The combined toluene solutions are washed with saturated NaCl solution, dried with Na2SO4, and the solvent is removed in vacuo. 335 g of diethyl 2,3,4,5-tetrafluorobenzoylmalonate are obtained as a crude product.

Workup

  1. additionare added dropwise at 50°-60° C
  2. temperatureThe mixture is then heated at 50°-60° C. for a further 1 hour
  3. waitto reach room temperature overnight
  4. temperaturewhile cooling in ice
  5. customThe phases are separated
  6. extractiontwo further extractions with toluene
  7. washThe combined toluene solutions are washed with saturated NaCl solution
  8. dry with materialdried with Na2SO4
  9. customthe solvent is removed in vacuo

Sources & evidence

ORD record
ord-3a92beeccaf84c05970fc797352922f0
Source dataset
uspto-grants-1986_07
Patent number
US04599334

Reaction notes

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