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

HRID 1461863Notes

Reaction equation

HRID 1461863 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 were suspended in 50 ml of anhydrous ethanol. 5 ml of carbon tetrachloride were added and, when the reaction had started, a mixture of 160 g of diethyl malonate, 100 ml of absolute ethanol and 400 ml of anhydrous ether was added dropwise, a vigorous reflux being observed. After the reaction had ceased, the mixture was heated at the boil for a further 2 hours and was cooled with dry ice/acetone at 315° C. to -10° C. and a solution of 227.5 g of 2,4-dichloro-5-fluoro-benzoyl chloride in 100 ml of absolute ether was slowly added dropwise at this temperature. The mixture was stirred for 1 hour at 0° C. to -5° C. and was allowed to reach room temperature overnight, and a mixture of 400 ml of ice-water and 25 ml of concentrated sulphuric acid was allowed to run in while cooling with ice. The phases were separated and were extracted twice with ether. The combined ether solutions were washed with saturated NaCl solution and dried with Na2SO4, and the solvent was stripped off in vacuo. 349.5 g of diethyl 2,4-dichloro-5-fluoro-benzoyl-malonate were obtained as the crude product.

Workup

  1. additionwas added dropwise
  2. temperaturea vigorous reflux
  3. temperaturethe mixture was heated at the boil for a further 2 hours
  4. waitto reach room temperature overnight
  5. temperaturewhile cooling with ice
  6. customThe phases were separated
  7. extractionwere extracted twice with ether
  8. washThe combined ether solutions were washed with saturated NaCl solution
  9. dry with materialdried with Na2SO4

Sources & evidence

ORD record
ord-4dd7d5c8140547d880148981a366b8ef
Source dataset
uspto-grants-1991_12
Patent number
US05077429

Reaction notes

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