Diethyl Malonate → Diethyl 2-vinylcyclopropane-1,1-dicarboxylate

HRID 1413995Notes

Reaction equation

HRID 1413995 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[CH2:12](Cl)/[CH:13]=[CH:14]/[CH2:15]Cl.[OH-].[K+]>[Cl-].C(C([NH3+])(C(=O)CCCCCCC)C(=O)CCCCCCC)(=O)CCCCCCC.C(Cl)Cl>[CH:13]([CH:14]1[CH2:15][C:2]1([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])=[CH2:12]

Participants

6

Reactant 3

HCID 7761Diethyl MalonateHCID 14797Potassium HydroxideHCID 6421971,4-Dichloro-2-butene, (2E)-

Product 1

HCID 111025Diethyl 2-vinylcyclopropane-1,1-dicarboxylateYield 77.9%

Reagents, catalysts & solvents 2

HCID 77620884Tricaprylylmethyl ammonium chlorideCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

To demonstrate the ability to vary the method of addition, diethyl malonate (160 g; 1.0 mol) was slowly charged to a reactor with external cooling means containing 137.5 g (1.10 mol) trans 1,4-dichlorobutene-2, 125 g (2.0 mol) flaked KOH (90%), 300 cc methylene chloride and 21 g (5 mol %) of tricaprylylmethylammonium chloride. The reaction mixture was stirred during the addition and temperature maintained at 25° C. with external cooling. At the completion of the reaction the resulting crude product obtained following the usual workup procedure was fractionally distilled and 165.3 g diethyl 2-vinylcyclopropane-1,1-dicarboxylate (77.9% yield) recovered. The reaction was repeated using 1/2 and 1/4 the volume of methylene chloride and yields were 77.4% and 72.3%, respectively. While the reaction does proceed when no solvent is employed, the yield of the diethyl ester product is less than optimum.

Workup

  1. additionwas slowly charged to a reactor
  2. temperaturewith external cooling
  3. customobtained
  4. distillationwas fractionally distilled

Sources & evidence

ORD record
ord-267cc3c872fc42b595b985452f1a6b36
Source dataset
uspto-grants-1981_02
Patent number
US04252739

Reaction notes

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