Diethyl Malonate → 2-ethenylcyclopropane-1,1-dicarboxylic acid

HRID 1413992Notes

Reaction equation

HRID 1413992 reaction equation
[OH-].[K+].[CH2:3](Cl)/[CH:4]=[CH:5]/[CH2:6]Cl.[C:9]([O:17]CC)(=[O:16])[CH2:10][C:11]([O:13]CC)=[O:12].[Cl-].C(C([NH3+])(C(=O)CCCCCCC)C(=O)CCCCCCC)(=O)CCCCCCC>C(Cl)Cl>[CH:4]([CH:5]1[CH2:6][C:10]1([C:9]([OH:17])=[O:16])[C:11]([OH:13])=[O:12])=[CH2:3]

Participants

6

Reactant 4

HCID 7761Diethyl MalonateHCID 14797Potassium Hydroxide2×HCID 6421971,4-Dichloro-2-butene, (2E)-HCID 77620884Tricaprylylmethyl ammonium chloride

Product 1

HCID 2859342-ethenylcyclopropane-1,1-dicarboxylic acidYield 76.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A reaction similar to that described in Example 6 was carried out using solid KOH on a larger scale as follows: To a stirred solution of 550 g (4.4 mol) trans 1,4-dichlorobutene-2, 640 g (4.0 mol) diethyl malonate, 80.7 g tricaprylylmethylammonium chloride in 2.4 liters methylene chloride were added over a one-hour period in small portions 498.7 g (8.0 mol) solid potassium hydroxide flakes (90%). The reaction was then heated to reflux for one hour. Potassium salts were removed by successive additions of water to the reaction mixture and siphoning off the aqueous layer until a total of 1.8 liters of water was added. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated and distilled at reduced pressure. The diethyl ester of 2-vinylcyclopropane-1,1-dicarboxylic acid was obtained in 76.8% yield.

Workup

  1. customA reaction similar to
  2. temperatureThe reaction was then heated
  3. temperatureto reflux for one hour
  4. customPotassium salts were removed by successive additions of water to the reaction mixture
  5. additionwas added
  6. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. distillationdistilled at reduced pressure

Sources & evidence

ORD record
ord-cba4c18c7b634fbe80b1b2fea51258bd
Source dataset
uspto-grants-1981_02
Patent number
US04252739

Reaction notes

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