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

HRID 2059091Notes

Reaction equation

HRID 2059091 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]>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[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 3

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 962WaterSolvent

Procedure

An aqueous solution (50%) of potassium hydroxide (168 g) was added dropwise to a vigorously stirred solution of 125 g (1.0 mol) trans 1,4-dichlorobutene-2, 80 g (0.5 mol) diethyl malonate and 3.2 g tricaprylmethylammonium chloride while maintaining the temperature at 25°-30° C. When the addition was complete, the mixture was stirred at ambient temperature for five hours and water then added to dissolve suspended salts. After separation of the phases followed by washing of the aqueous phase three times with ethyl ether, the organic portion was distilled to obtain 21.3 g 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 also consistent with the desired compound.

Workup

  1. temperaturewhile maintaining the temperature at 25°-30° C
  2. additionWhen the addition
  3. dissolutionto dissolve
  4. customAfter separation of the phases
  5. washby washing of the aqueous phase three times with ethyl ether
  6. distillationthe organic portion was distilled

Sources & evidence

ORD record
ord-0ce41249a1da44f9a431eca5e3efeece
Source dataset
uspto-grants-1982_03
Patent number
US04321406

Reaction notes

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