Sulfuric Acid → Diethyl (2-chloro-4,5-difluorobenzoyl)propanedioate

HRID 982205Notes

Reaction equation

HRID 982205 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].[Cl:13][C:14]1[CH:22]=[C:21]([F:23])[C:20]([F:24])=[CH:19][C:15]=1[C:16](Cl)=[O:17].S(=O)(=O)(O)O>C1(C)C=CC=CC=1.C(O)C.C(Cl)(Cl)(Cl)Cl>[Cl:13][C:14]1[CH:22]=[C:21]([F:23])[C:20]([F:24])=[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 5462224MagnesiumHCID 101982172-Chloro-4,5-difluorobenzoyl chloride

Product 1

HCID 14425827Diethyl (2-chloro-4,5-difluorobenzoyl)propanedioateYield 99.9%

Reagents, catalysts & solvents 3

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

Procedure

To 6.34 g of magnesium turnings, 13 cc of absolute ethanol and 1.2 ml of carbon tetrachloride were added, and the mixture was stirred. After the initiation of the reaction, a solution comprising 39.9 g of diethyl malonate, 22 cc of absolute ethanol and 75 cc of toluene was dropwise added thereto at a temperature of from 50° to 70° C. After the dropwise addition, the mixture was stirred for two hours. Then, the reaction solution was cooled to -10° to -5° C., and a solution comprising 50 g of 2-chloro-4,5-difluorobenzoyl chloride and 15 ml of toluene was dropwise added thereto. Then, the mixture was stirred for two hours. A dilute sulfuric acid aqueous solution cooled with ice was added thereto, and the content was dissolved, subjected to phase separation and extracted three times with 60 cc of toluene. The organic phase was washed with water, then dried over anhydrous magnesium sulfate and concentrated to obtain 79.2 g of the desired product as a slightly yellow oily substance.

Workup

  1. customAfter the initiation of the reaction
  2. additionwas dropwise added
  3. customof from 50° to 70° C
  4. additionAfter the dropwise addition
  5. stirringthe mixture was stirred for two hours
  6. temperatureThen, the reaction solution was cooled to -10° to -5° C.
  7. additionwas dropwise added
  8. stirringThen, the mixture was stirred for two hours
  9. additionwas added
  10. dissolutionthe content was dissolved
  11. customsubjected to phase separation
  12. extractionextracted three times with 60 cc of toluene
  13. washThe organic phase was washed with water
  14. dry with materialdried over anhydrous magnesium sulfate
  15. concentrationconcentrated

Sources & evidence

ORD record
ord-352d45465eab424dbd70b4aaa0fa7afa
Source dataset
uspto-grants-1991_02
Patent number
US04994610

Reaction notes

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