Hydrochloric Acid → Diallyl 2-(4-cyanobenzyl)malonate

HRID 1913781ノート

反応式

HRID 1913781 の反応式
[H-].[Na+].[C:3]([O:12][CH2:13][CH:14]=[CH2:15])(=[O:11])[CH2:4][C:5]([O:7][CH2:8][CH:9]=[CH2:10])=[O:6].[H][H].Cl[CH2:19][C:20]1[CH:27]=[CH:26][C:23]([C:24]#[N:25])=[CH:22][CH:21]=1.Cl>O1CCOCC1.O>[C:24]([C:23]1[CH:26]=[CH:27][C:20]([CH2:19][CH:4]([C:5]([O:7][CH2:8][CH:9]=[CH2:10])=[O:6])[C:3]([O:12][CH2:13][CH:14]=[CH2:15])=[O:11])=[CH:21][CH:22]=1)#[N:25]

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 701274-(Chloromethyl)benzonitrileHCID 228227Diallyl malonateHCID 178418361HCID 178418361、化合物

生成物 1

HCID 57831332Diallyl 2-(4-cyanobenzyl)malonate

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 312751,4-Dioxane溶媒2 回

実験手順

19.79 g (0.494 mol) of sodium hydride are added in portions to a solution of 121.5 g (0.659 mol) of diallyl malonate in 1.5 litres of dioxane at 0° C. (caution: evolution of hydrogen). After warming to room temperature, the mixture is stirred at 40° C. for 1 hour. Subsequently, 50 g (0.329 mol) of 4-chloromethylbenzonitrile, dissolved in 500 ml of dioxane, are slowly added dropwise at 40° C., and the reaction solution is stirred at 110° C. overnight. After cooling to room temperature, the reaction mixture is added to 1200 ml of water. Care must be taken during this that the pH remains <7 (if necessary, a few ml of 1 M hydrochloric acid are metered in until the pH is about 2). The mixture is then extracted three times with ethyl acetate, and the combined organic phases are washed with saturated sodium chloride solution and dried over sodium sulphate. After filtration, the solvent is evaporated to dryness in vacuo. Excess diallyl malonate is then removed by high vacuum distillation (boiling point: 57° C., 0.074 mbar). The distillation residue is purified by flash chromatography on silica gel (mobile phase: petroleum ether/ethyl acetate 20:1). 67 g (0.22 mol, 67% of theory) of a colourless solid are obtained.

後処理

  1. additionare slowly added dropwise at 40° C.
  2. stirringthe reaction solution is stirred at 110° C. overnight
  3. temperatureAfter cooling to room temperature
  4. extractionThe mixture is then extracted three times with ethyl acetate
  5. washthe combined organic phases are washed with saturated sodium chloride solution
  6. dry with materialdried over sodium sulphate
  7. filtrationAfter filtration
  8. customthe solvent is evaporated to dryness in vacuo
  9. customExcess diallyl malonate is then removed by high vacuum distillation (boiling point: 57° C., 0.074 mbar)
  10. distillationThe distillation residue is purified by flash chromatography on silica gel (mobile phase: petroleum ether/ethyl acetate 20:1)
  11. custom67 g (0.22 mol, 67% of theory) of a colourless solid are obtained

出典と根拠

ORDレコード
ord-4939b6cb947a4bb2a0ca7ba06d1fb66a
出典データセット
uspto-grants-2013_12
特許番号
US08609727B2

反応ノート

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