Sulfuric Acid → Diethyl 2-(2,4-dichloro-5-fluorobenzoyl)malonate

HRID 637953Notes

Reaction equation

HRID 637953 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.[Cl:20][C:21]1[CH:29]=[C:28]([Cl:30])[C:27]([F:31])=[CH:26][C:22]=1[C:23](Cl)=[O:24].S(=O)(=O)(O)O>C(O)C.CCOCC.C(Cl)(Cl)(Cl)Cl>[Cl:20][C:21]1[CH:29]=[C:28]([Cl:30])[C:27]([F:31])=[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 27368212,4-Dichloro-5-fluorobenzoyl chlorideHCID 5462224MagnesiumHCID 18522661Acetone cardice

Product 1

HCID 13326819Diethyl 2-(2,4-dichloro-5-fluorobenzoyl)malonateYield 99.6%

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent2×HCID 3283Diethyl EtherSolvent2×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 up, a mixture of 160 g of diethyl malonate, 100 ml of absolute ethanol and 400 ml of anhydrous ether is added dropwise, vigorous reflux being observed. After the reaction has moderated, the mixture is heated to boiling for 2 hours, then cooled down to -5° C. to -10° C. with dry ice/acetone and, at this temperature, a solution of 227.5 g of 2,4-dichloro-5-fluorobenzoyl chloride (1) in 100 ml of absolute ether is slowly added dropwise. The mixture is stirred at 0° to -5° C. for 1 hour, allowed to reach room temperature overnight and, while cooling in ice, a mixture of 400 ml of ice-water and 25 ml of concentrated sulphuric acid is allowed to run in. The phases are separated and the aqueous phase is extracted twice more with ether. The combined ether solutions are washed with saturated NaCl solution, dried with Na2SO4 and the solvent is removed in vacuo. 349.5 g of diethyl 2,4-dichloro-5-fluorobenzoylmalonate (3) are obtained as a reaction product.

Workup

  1. additionis added dropwise
  2. temperaturevigorous reflux
  3. temperaturethe mixture is heated
  4. waitto reach room temperature overnight
  5. temperaturewhile cooling in ice
  6. customThe phases are separated
  7. extractionthe aqueous phase is extracted twice more with ether
  8. washThe combined ether solutions are washed with saturated NaCl solution
  9. dry with materialdried with Na2SO4
  10. customthe solvent is removed in vacuo

Sources & evidence

ORD record
ord-73cb54668556429d990efd919a97905d
Source dataset
uspto-grants-1985_12
Patent number
US04559342

Reaction notes

Loading…