Diethyl Malonate → 1,1-Diethyl cyclopent-3-ene-1,1-dicarboxylate

HRID 1085805Notes

Reaction equation

HRID 1085805 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Li+].[H][H].Cl[CH2:17]/[CH:18]=[CH:19]\[CH2:20]Cl>CN(C)C=O.CCOCC.CCCCCC.O>[C:2]1([C:3]([O:5][CH2:6][CH3:7])=[O:4])([C:1]([O:9][CH2:10][CH3:11])=[O:8])[CH2:20][CH:19]=[CH:18][CH2:17]1

Participants

9

Reactant 4

HCID 7761Diethyl MalonateHCID 62714Lithium hydrideHCID 64321151,4-Dichloro-cis-2-buteneHCID 178418361HCID 178418361, compound

Product 1

HCID 109875691,1-Diethyl cyclopent-3-ene-1,1-dicarboxylate

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolventHCID 8058HexaneSolvent

Procedure

To a stirred solution of 160 g of diethyl malonate in 1.5 l of dry dimethylformamide at 0° C. under nitrogen was slowly added 30 g of lithium hydride. After the evolution of hydrogen ceased (2 hours) 143 g of cis-1,4-dichloro-2-butene was slowly added and the mixture allowed to come to room temperature. After 72 hours, the mixture was diluted with a mixture of ether and hexane (1:4) and poured into water. The organic layer was washed with water and brine before drying over magnesium sulfate. Distillation gave diethyl 3-cyclopentene-1,1-dicarboxylate, bp 70°-80° C./0.1 mm, containing a small amount (~10%) of diethyl 2-vinylcyclopropane-1,1-dicarboxylate.

Workup

  1. customat 0° C.
  2. additionwas slowly added
  3. customto come to room temperature
  4. washThe organic layer was washed with water and brine
  5. dry with materialbefore drying over magnesium sulfate
  6. distillationDistillation

Sources & evidence

ORD record
ord-f23345d95300427987ed83da2cfa58e4
Source dataset
uspto-grants-1991_04
Patent number
US05011846

Reaction notes

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