Potassium Hydroxide → Diisopropyl 2-vinylcyclopropane-1,1-dicarboxylate

HRID 1413988

Reaktionsgleichung

Reaktionsgleichung von HRID 1413988
C(C1CC1)=C.[CH2:6](Cl)/[CH:7]=[CH:8]/[CH2:9]Cl.[C:12]([O:21][CH:22]([CH3:24])[CH3:23])(=[O:20])[CH2:13][C:14]([O:16][CH:17]([CH3:19])[CH3:18])=[O:15].[Cl-].C(C([NH3+])(C(=O)CCCCCCC)C(=O)CCCCCCC)(=O)CCCCCCC.[OH-].[K+]>O>[CH:7]([CH:8]1[CH2:9][C:13]1([C:14]([O:16][CH:17]([CH3:19])[CH3:18])=[O:15])[C:12]([O:21][CH:22]([CH3:24])[CH3:23])=[O:20])=[CH2:6]

Komponenten

7

Edukt 5

HCID 14797Potassium HydroxideHCID 83223Diisopropyl malonateHCID 136498EthenylcyclopropaneHCID 6421971,4-Dichloro-2-butene, (2E)-HCID 77620884Tricaprylylmethyl ammonium chloride

Produkt 1

HCID 13137099Diisopropyl 2-vinylcyclopropane-1,1-dicarboxylateAusbeute 153,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Versuchsvorschrift

To illustrate the preparation of vinylcyclopropane derivatives via malonic ester condensation in an aqueous medium, the following experiment was conducted: To a flask provided with a stirrer and containing 125 g (1.0 mol) trans 1,4-dichlorobutene-2, 94 g (0.50 mol) diisopropyl malonate and 3.2 g (1.63 mol percent based on the malonate ester) tricaprylylmethylammonium chloride were added dropwise over a 30-minute perid with vigorous stirring 168 g 50% aqueous potassium hydroxide solution. Cooling was provided to maintain the reaction temperature at 25°-30° C. After five hours the reaction mixture was poured into water and extracted three times with ethyl ether. The combined etheral layers were dried over magnesium sulfate, filtered and concentrated to afford 184 g (67.2% yield) diisopropyl 2-vinylcyclopropane-1,1-dicarboxylate. Bp 77°-78° C.(0.5 mm); nD24° 1.4482. Infrared and proton nmr spectra were consistent with the desired structure. Similar results were obtained using other quaternary ammonium compounds, however, when the onium compound was omitted the reaction did not proceed.

Aufarbeitung

  1. customTo a flask provided with a stirrer
  2. additionwere added dropwise over a 30-minute perid
  3. temperatureCooling
  4. customwas provided
  5. temperatureto maintain the reaction temperature at 25°-30° C
  6. extractionextracted three times with ethyl ether
  7. dry with materialThe combined etheral layers were dried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-a28b7e9d3c8e42619d832a75bdd71ed9
Quelldatensatz
uspto-grants-1981_02
Patentnummer
US04252739

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