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

HRID 1413991Notes

Reaction equation

HRID 1413991 reaction equation
[OH-].[K+].[CH2:3](Cl)/[CH:4]=[CH:5]/[CH2:6]Cl.[C:9]([O:17][CH2:18][CH3:19])(=[O:16])[CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12].[Cl-]>O>[CH:4]([CH:5]1[CH2:6][C:10]1([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:9]([O:17][CH2:18][CH3:19])=[O:16])=[CH2:3]

Participants

6

Reactant 4

HCID 312ChlorideHCID 7761Diethyl MalonateHCID 14797Potassium HydroxideHCID 6421971,4-Dichloro-2-butene, (2E)-

Product 1

HCID 111025Diethyl 2-vinylcyclopropane-1,1-dicarboxylateYield 20.1%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Diethyl 2-vinylcyclopropane-1,1-dicarboxylate was prepared as follows: Fifty percent aqueous potassium hydroxide solutin (168 g) was added dropwise to a vigorously stirred solution of 125 g (1.0 mol) trans 1,4-dichlorobutene-2, 80 g (0.50 mol) diethyl malonate and 3.2 g tricaprylymethylammonium chloride while the temperature was maintained at 25°-30° C. When the addition was complete, the reaction mixture was stirred at ambient temperature for an additional five hours. Water was then added to the reaction mixture to completely dissolve the suspended salts in the aqueous phase. The phase layers were separated and the aqueous portion extracted three times with ethyl ether. Distillation of the combined organic solutions gave 21.3 g of the desired diethyl 2-vinylcyclopropane-1,1-dicarboxylate. Bp 64°-66° C. (0.15 mm); nD27° 1.4512; [lit.bp 69°-72° C. (0.5 mm); nD19° 1.4528]. Infrared and proton nmr spectra were consistent with the desired compound. Upon acidification and extraction of the aqueous phase, 19.6 g 2-vinylcyclopropane-1,1-dicarboxylic acid was recovered so that the overall yield of cyclized product was 45.3%.

Workup

  1. customDiethyl 2-vinylcyclopropane-1,1-dicarboxylate was prepared
  2. temperaturewas maintained at 25°-30° C
  3. additionWhen the addition
  4. dissolutionto completely dissolve the suspended salts in the aqueous phase
  5. customThe phase layers were separated
  6. extractionthe aqueous portion extracted three times with ethyl ether
  7. distillationDistillation of the combined organic solutions

Sources & evidence

ORD record
ord-26e15c2c8b59410c9e6897880fcb7e9d
Source dataset
uspto-grants-1981_02
Patent number
US04252739

Reaction notes

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