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

HRID 1413988ノート

反応式

HRID 1413988 の反応式
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]

参加物

7

反応物 5

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

生成物 1

HCID 13137099Diisopropyl 2-vinylcyclopropane-1,1-dicarboxylate収率 153.1%

試薬・触媒・溶媒 1

HCID 962Water溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-a28b7e9d3c8e42619d832a75bdd71ed9
出典データセット
uspto-grants-1981_02
特許番号
US04252739

反応ノート

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