Sulfuric Acid → Diethyl (2,3-dichloro-4,5-difluorobenzoyl)propanedioate

HRID 2232632Notes

Reaction equation

HRID 2232632 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[C:22]([Cl:23])=[C:21]([F:24])[C:20]([F:25])=[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[C:22]([Cl:23])=[C:21]([F:24])[C:20]([F:25])=[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 10999320Benzoyl chloride, 2,3-dichloro-4,5-difluoro-

Product 1

HCID 14071801Diethyl (2,3-dichloro-4,5-difluorobenzoyl)propanedioateYield 107.3%

Reagents, catalysts & solvents 3

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

Procedure

Magnesium turnings (0.77 g) and carbon tetrachloride (0.4 ml) was added to absolute ethanol (5.3 ml). To the stirring suspension was added a solution of diethyl malonate (4.89 g) and absolute ethanol (8.5 ml) in toluene (21.3 ml) dropwise during 40 minutes at 20° to 40° C. The mixture was stirred at 50° to 60° C. for 2 hours, and then cooled in an acetone-dry ice bath. A solution of 2,3-dichloro-4,5-difluorobenzoyl chloride (6.00 g) in anhydrous toluene (7.1 ml) was added dropwise to the resulting solution at -18° to -13° C. during 10 minutes. The mixture was warmed gradually to room temperature during 2 hours and then mixed with ice water (17 ml) containing concentrated sulfuric acid (1.1 ml). The resulting organic layer was collected and the water layer was extracted with toluene. The combined organic layer was washed with water, dried over anhydrous sodium sulfate and then concentrated to give the title compound (9.68 g) as pale yellow oil.

Workup

  1. temperaturecooled in an acetone-dry ice bath
  2. customThe resulting organic layer was collected
  3. extractionthe water layer was extracted with toluene
  4. washThe combined organic layer was washed with water
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-bf7c0540b87742ffbc083bbae5ab2b3d
Source dataset
uspto-grants-1988_11
Patent number
US04788320

Reaction notes

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