Sulfuric Acid → Diethyl 2-chloro-3-methyl-4,5-difluorobenzoylmalonate

HRID 2107582Notes

Reaction equation

HRID 2107582 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]([CH3:23])=[C:21]([F:24])[C:20]([F:25])=[CH:19][C:15]=1[C:16](Cl)=[O:17].S(=O)(=O)(O)O>C(O)C.C(Cl)(Cl)(Cl)Cl.C1(C)C=CC=CC=1.O>[Cl:13][C:14]1[C:22]([CH3:23])=[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

9

Reactant 4

HCID 1118Sulfuric AcidHCID 7761Diethyl MalonateHCID 5462224MagnesiumHCID 156318252-Chloro-4,5-difluoro-3-methylbenzoyl chloride

Product 1

HCID 15631826Diethyl 2-chloro-3-methyl-4,5-difluorobenzoylmalonate

Reagents, catalysts & solvents 4

HCID 5943Carbon TetrachlorideCatalystHCID 702EthanolSolvent2×HCID 962WaterSolventHCID 1140TolueneSolvent2×

Procedure

Separately, metallic magnesium (0.38 g) is suspended in anhydrous ethanol (0.8 ml) and thereto is added a few drops of carbon tetrachloride. When the reaction is started, a mixture of diethyl malonate (2.3 ml), anhydrous ethanol (1.5 ml) and anhydrous toluene (6 ml) is added portionwise at 50°-60° C. Thereto is added dropwise a solution of the above 2-chloro-4,5-difluoro-3-methylbenzoyl chloride (3.3 g) in anhydrous toluene (5 ml) at 0° C. After the addition, the mixture is stirred at room temperature for 30 minutes. To the reaction mixture is added a mixture of conc. sulfuric acid (0.4 ml) and water (8 ml) and the mixture is extracted with diethyl ether. The extract is dried over magnesium sulfate and the solvent is then distilled off to give diethyl 2-chloro-3-methyl-4,5-difluorobenzoylmalonate (5.1 g).

Workup

  1. additionis added portionwise at 50°-60° C
  2. additionAfter the addition
  3. additionTo the reaction mixture is added
  4. extractionthe mixture is extracted with diethyl ether
  5. dry with materialThe extract is dried over magnesium sulfate
  6. distillationthe solvent is then distilled off

Sources & evidence

ORD record
ord-030889b539a940a9958e97de0c12d386
Source dataset
uspto-grants-1990_06
Patent number
US04935420

Reaction notes

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