Acetone → Diethyl isopropylidenemalonate

HRID 2209428Notes

Reaction equation

HRID 2209428 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].C(OC(=O)C)(=O)C.[CH3:19][C:20]([CH3:22])=O>C1C=CC=CC=1.[Cl-].[Zn+2].[Cl-]>[C:20](=[C:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])([CH3:22])[CH3:19]

Participants

6

Reactant 3

HCID 180AcetoneHCID 7761Diethyl MalonateHCID 7918Acetic Anhydride

Product 1

HCID 81255Diethyl isopropylidenemalonateYield 44.7%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 241BenzeneSolvent

Procedure

A reaction mixture of 200 g (1.25 mol) of diethyl malonate, 159.51 g (1.56 mol) of acetic anhydride, 108.9 g (1.87 mol) of acetone, and 25.5 g (0.187 mol) of zinc chloride placed in a 1000 ml round bottom flask was allowed to reflux for 20 hours. The reaction mixture was cooled, diluted with 200 ml of benzene, and the resulting mixture was washed with water (4×250 ml). The combined aqueous layer was extracted with benzene (2×50 ml) and the organic layers were combined. After removing benzene in vacuo, the mixture was distilled twice (Vigreux distilling column--10") to afford 111.8 g (44.7%--crude) of diethyl isopropylidenemalonate contains a trace of diethyl malonate), b.p. 80° C./0.5 mm.

Workup

  1. customplaced in a 1000 ml round bottom flask
  2. temperatureto reflux for 20 hours
  3. temperatureThe reaction mixture was cooled
  4. washthe resulting mixture was washed with water (4×250 ml)
  5. extractionThe combined aqueous layer was extracted with benzene (2×50 ml)
  6. customAfter removing benzene in vacuo
  7. distillationthe mixture was distilled twice
  8. distillation(Vigreux distilling column--10")

Sources & evidence

ORD record
ord-bd858b09828c4b109a75ee6ca594f1f2
Source dataset
uspto-grants-1995_10
Patent number
US05455248

Reaction notes

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