Sulfuric Acid → Diethyl dimethylmalonate

HRID 2400051Notes

Reaction equation

HRID 2400051 reaction equation
S(=O)(=O)(O)O.[CH3:6][C:7]([CH3:14])([C:11]([OH:13])=[O:12])[C:8]([OH:10])=[O:9].[CH2:15](O)[CH3:16].[C:18]1(C)C=CC=C[CH:19]=1>>[CH2:18]([O:9][C:8](=[O:10])[C:7]([CH3:14])([CH3:6])[C:11]([O:13][CH2:15][CH3:16])=[O:12])[CH3:19]

Participants

4

Reactant 3

HCID 1118Sulfuric AcidHCID 11686Dimethylmalonic acidHCID 21863594Toluene ethanol

Product 1

HCID 15382Diethyl dimethylmalonate

Procedure

0.023 ml of concentrated sulfuric acid are cautiously added to a solution of 4 g of 2,2-dimethylmalonic acid in 30 ml of a 1:2 absolute ethanol/toluene mixture. The reaction mixture is refluxed, distilling the azeotropic water/toluene mixture and adding every few an ethanol/toluene mixture. After 3 hours, the reaction mixture is added with 50 ml of water and extracted with ethyl acetate (3×15 ml). The combined organic extracts are dried over sodium sulfate and solvent is evaporated off under reduced pressure. The residue is purified by silica gel chromatography (eluent 2:1 hexane/AcOEt). 3.3 g of 2,2-dimethylmalonic acid diethyl ester are obtained.

Workup

  1. temperatureThe reaction mixture is refluxed
  2. distillationdistilling the azeotropic water/toluene mixture
  3. additionadding every few an ethanol/toluene mixture
  4. additionthe reaction mixture is added with 50 ml of water
  5. extractionextracted with ethyl acetate (3×15 ml)
  6. dry with materialThe combined organic extracts are dried over sodium sulfate and solvent
  7. customis evaporated off under reduced pressure
  8. customThe residue is purified by silica gel chromatography (eluent 2:1 hexane/AcOEt)

Sources & evidence

ORD record
ord-af9b44e490234645a76b38353eed94d9
Source dataset
uspto-grants-1995_09
Patent number
US05453423

Reaction notes

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