Dimethyl malonate → 1,1-Dimethyl 2-ethenylcyclopropane-1,1-dicarboxylate

HRID 1702217

反応式

HRID 1702217 の反応式
[Na].[C:2]([O:9][CH3:10])(=[O:8])[CH2:3][C:4]([O:6][CH3:7])=[O:5].C([O-])(=O)CC([O-])=O.[Na+].[Na+].CO.[Na]C([Na])(C(O)=O)C(O)=O.[CH2:31](Cl)/[CH:32]=[CH:33]/[CH2:34]Cl>C(O)C.CO>[CH:32]([CH:33]1[CH2:34][C:3]1([C:2]([O:9][CH3:10])=[O:8])[C:4]([O:6][CH3:7])=[O:5])=[CH2:31]

参加物

8

反応物 5

HCID 7943Dimethyl malonateHCID 8865Malonic acid, disodium saltHCID 6421971,4-Dichloro-2-butene, (2E)-HCID 5360545SodiumHCID 178502909HCID 178502909、化合物

生成物 1

HCID 104649921,1-Dimethyl 2-ethenylcyclopropane-1,1-dicarboxylate収率 55.6%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 887Methanol溶媒

反応条件

温度
60 °C

実験手順

To a solution of 36.6 g (1.6 g-atom) of sodium in 500 ml of anhydrous ethanol was added 105.5 g (0.80 mol) of dimethyl malonate. After several minutes, while maintaining the temperature at 60° C., 250 ml anhydrous methanol was added to solubilize the precipated sodium malonate salt. The freshly prepared disodiomalonate methanol solution was added to 100.0 g (0.80 mol) trans 1,4-dichlorobutene-2 heated to 60°-70° C. at a rate to allow a gentle reflux in the condenser. When the addition was completed, the reaction mixture was refluxed with stirring for an additional 4 hours. The reaction mixture was then cooled to ambient temperature, filtered and the resulting filtrate concentrated. Distillation of the crude product under reduced pressure afforded 82 g (44.5%) of the desired product dimethyl 2-vinylcyclopropane-1,1-dicarboxylate. B.p. 73°-78° at 1.25 mm Hg; nD24 1.4612; [lit. B.p. 71°- 73° (1 mm); nD25 1.4602].

後処理

  1. waitAfter several minutes
  2. temperatureheated to 60°-70° C. at a rate
  3. temperaturea gentle reflux in the condenser
  4. additionWhen the addition
  5. temperaturethe reaction mixture was refluxed
  6. temperatureThe reaction mixture was then cooled to ambient temperature
  7. filtrationfiltered
  8. concentrationthe resulting filtrate concentrated
  9. distillationDistillation of the crude product under reduced pressure

出典と根拠

ORDレコード
ord-a03383b0c0504cceb7a20be6c434e907
出典データセット
uspto-grants-1983_04
特許番号
US04380656

関連ノート

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