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

HRID 1284517Notes

Reaction equation

HRID 1284517 reaction equation
[Mg].C([C:4](CC)([C:8]([O-:10])=[O:9])[C:5]([O-:7])=[O:6])C.C(=O)=O.C[C:17]([CH3:19])=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.[CH2:37](O)[CH3:38]>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:4]([C:8]([O:10][CH2:17][CH3:19])=[O:9])[C:5]([O:7][CH2:37][CH3:38])=[O:6])=[O:24]

Participants

9

Reactant 6

HCID 702Ethanol2×HCID 1118Sulfuric AcidHCID 27368212,4-Dichloro-5-fluorobenzoyl chlorideHCID 5462224MagnesiumHCID 69515632,2-DiethylpropanedioateHCID 18522661Acetone cardice

Product 1

HCID 13326819Diethyl 2-(2,4-dichloro-5-fluorobenzoyl)malonate

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 5943Carbon TetrachlorideSolvent

Procedure

24.3 g of magnesium fillings 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 diethylmalonate, 100 ml of absolute ethanol and 400 ml of anhydrous ether is added dropwise, whereupon vigorous reflux is to be observed. After the reaction has subsided, the mixture is heated at the boiling point for a further 2 hours and cooled to -5° C. to -10° C. with dry ice/acetone, and a solution of 227.5 g of 2,4-dichloro-5-fluoro-benzoyl chloride (1) in 100 ml of absolute ether is slowly added dropwise at this temperature. The mixture is stirred at 0° C. to -5° C. for 1 hour and allowed to come to room temperature overnight, and a mixture of 400 ml of ice-water and 25 ml of concentrated sulphuric acid is run in, while cooling with ice. The phases are separated and subsequent extraction with ether is carried out twice. The combined ether solutions are washed with saturated NaCl solution and dried with Na2SO4 and the solvent is stripped off in vacuo. 349.5 g of diethyl 2,4-dichloro-5-fluoro-benzoyl-malonate (3) are obtained as the crude product.

Workup

  1. additionis added dropwise
  2. temperaturewhereupon vigorous reflux
  3. temperaturethe mixture is heated at the boiling point for a further 2 hours
  4. waitto come to room temperature overnight
  5. temperaturewhile cooling with ice
  6. customThe phases are separated
  7. extractionsubsequent extraction with ether
  8. washThe combined ether solutions are washed with saturated NaCl solution
  9. dry with materialdried with Na2SO4

Sources & evidence

ORD record
ord-c8b4adae09e7400b8bd4c6f8ce89d675
Source dataset
uspto-grants-1986_01
Patent number
US04563448

Reaction notes

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