Acetone → Diethyl isopropylidenemalonate

HRID 867764Notes

Reaction equation

HRID 867764 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[CH3:12][C:13]([CH3:15])=O.C(OC(=O)C)(=O)C>[Cl-].[Zn+2].[Cl-].C1C=CC=CC=1>[C:13](=[C:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])([CH3:15])[CH3:12]

Participants

6

Reactant 3

HCID 180AcetoneHCID 7761Diethyl MalonateHCID 7918Acetic Anhydride

Product 1

HCID 81255Diethyl isopropylidenemalonateYield 41%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 241BenzeneSolvent

Procedure

There were placed diethyl malonate (133 g, 0.83 mol), acetone (72 g, 1.24 mol), acetic anhydride (106 g, 1.05 mol) and zinc chloride (17.0 g, 0.125 mmol in a 500 ml three neck flask. After 24 hour reflux, benzene (200 ml) was added and the reaction mixture was washed with water (100 ml×4). The aqueous layer was further extracted with benzene (50 ml×2). The organic layers were combined and concentrated. The residue was distilled under reduced pressure to give oily product, diethyl isopropylidenemalonate (68.0 g, 0.34 mol, 41.0%, b.p.: 112° C./9 mmHg). The structure was confirmed by the following data.

Workup

  1. temperatureAfter 24 hour reflux
  2. washthe reaction mixture was washed with water (100 ml×4)
  3. extractionThe aqueous layer was further extracted with benzene (50 ml×2)
  4. concentrationconcentrated
  5. distillationThe residue was distilled under reduced pressure

Sources & evidence

ORD record
ord-1289baf465d846f9ae83a2015a914546
Source dataset
uspto-grants-1988_10
Patent number
US04775692

Reaction notes

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