Sulfuric Acid → Diethyl 2-(3-bromo-2-chloro-4,5-difluorobenzoyl)malonate

HRID 2232634Notes

Reaction equation

HRID 2232634 reaction equation
[O-]CC.[Mg+2].[O-]CC.[C:8]([O:16][CH2:17][CH3:18])(=[O:15])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11].[Br:19][C:20]1[C:21]([Cl:31])=[C:22]([CH:26]=[C:27]([F:30])[C:28]=1[F:29])[C:23](Cl)=[O:24].S(=O)(=O)(O)O>C1(C)C=CC=CC=1>[Br:19][C:20]1[C:21]([Cl:31])=[C:22]([CH:26]=[C:27]([F:30])[C:28]=1[F:29])[C:23]([CH:9]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:8]([O:16][CH2:17][CH3:18])=[O:15])=[O:24]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 7761Diethyl MalonateHCID 164963Magnesium ethanolateHCID 140717973-Bromo-2-chloro-4,5-difluorobenzoyl chloride

Product 1

HCID 14071798Diethyl 2-(3-bromo-2-chloro-4,5-difluorobenzoyl)malonateYield 104.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

To the magnesium ethoxide (3.93 g) suspension was added a solution of diethyl malonate (4.65 g) in anhydrous toluene (30 ml) dropwise during 25 minutes at 20° to 25° C. The mixture was stirred at 50° to 60° C. for 3 hours, and then cooled in an acetone-dry ice bath. A solution of 3-bromo-2-chloro-4,5-difluorobenzoyl chloride (7.65 g) in anhydrous toluene (15 ml) was added dropwise to the resulting solution at -16° to 0° C. during 25 minutes. The mixture was stirred for 2.5 hours below 0° C., then further stirred at room temperature for 40 minutes, and then mixed with ice water (15 ml) containing concentrated sulfuric acid (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 (11.44 g) as pale yellow oil.

Workup

  1. temperaturecooled in an acetone-dry ice bath
  2. stirringThe mixture was stirred for 2.5 hours below 0° C.
  3. stirringfurther stirred at room temperature for 40 minutes
  4. customThe resulting organic layer was collected
  5. extractionthe water layer was extracted with toluene
  6. washThe combined organic layer was washed with water
  7. dry with materialdried over anhydrous sodium sulfate
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-037f4d372bad4e72a30ad8f78fd723e9
Source dataset
uspto-grants-1988_11
Patent number
US04788320

Reaction notes

Loading…