Malonic Acid → dimenthyl malonate

HRID 2188498Notes

Reaction equation

HRID 2188498 reaction equation
[C:1]([OH:7])(=[O:6])[CH2:2][C:3]([OH:5])=[O:4].[CH:8]1([CH3:18])[CH2:13][CH2:12][CH:11]([CH:14]([CH3:16])[CH3:15])[CH:10](O)[CH2:9]1.S(=O)(=O)(O)O.O>C1(C)C=CC=CC=1>[C:1]([O:7][CH:10]1[CH:11]([CH:14]([CH3:16])[CH3:15])[CH2:12][CH2:13][CH:8]([CH3:18])[CH2:9]1)(=[O:6])[CH2:2][C:3]([O:5][CH:10]1[CH:11]([CH:14]([CH3:16])[CH3:15])[CH2:12][CH2:13][CH:8]([CH3:18])[CH2:9]1)=[O:4]

Participants

6

Reactant 4

HCID 867Malonic AcidHCID 962WaterHCID 1118Sulfuric AcidHCID 1254Menthol

Product 1

HCID 586745dimenthyl malonateYield 76.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Malonic acid (22.2 g, 0.213 mol) and menthol (70 g, 0.448 mol) are brought to reflux for 6 hours in 100 ml of toluene in the presence of 2 ml of concentrated sulfuric acid in a reactor surmounted by a Dean & Stark apparatus. The water formed is removed by azeotropic distillation. The organic phase is washed 3 times with water and is dried over sodium sulfate. The excess menthol is removed by distillation under vacuum (140° C. under 0.6 hPa). The residue is treated with animal charcoal in isopropanol at reflux. After filtering, rinsing and evaporating the solvent, 61.8 g (Yield 76%) of dimenthyl malonate are obtained in the form of a yellow oil which is used as is in the following stage.

Workup

  1. customis removed by azeotropic distillation
  2. washThe organic phase is washed 3 times with water
  3. dry with materialis dried over sodium sulfate
  4. customThe excess menthol is removed by distillation under vacuum (140° C. under 0.6 hPa)
  5. additionThe residue is treated with animal charcoal in isopropanol
  6. temperatureat reflux
  7. filtrationAfter filtering
  8. washrinsing

Sources & evidence

ORD record
ord-3b94b3e9be8e4262a89543044da55715
Source dataset
uspto-grants-2012_12
Patent number
US08323624B2

Reaction notes

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