Sodium hydride → Diallyl 2-[2-(4-cyanophenyl)ethyl]malonate

HRID 1921890Notes

Reaction equation

HRID 1921890 reaction equation
[H-].[Na+].[H][H].[C:5]([O:14][CH2:15][CH:16]=[CH2:17])(=[O:13])[CH2:6][C:7]([O:9][CH2:10][CH:11]=[CH2:12])=[O:8].Br[CH2:19][CH2:20][C:21]1[CH:28]=[CH:27][C:24]([C:25]#[N:26])=[CH:23][CH:22]=1.[Cl-].[NH4+]>O1CCOCC1>[C:25]([C:24]1[CH:27]=[CH:28][C:21]([CH2:20][CH2:19][CH:6]([C:7]([O:9][CH2:10][CH:11]=[CH2:12])=[O:8])[C:5]([O:14][CH2:15][CH:16]=[CH2:17])=[O:13])=[CH:22][CH:23]=1)#[N:26]

Participants

7

Reactant 5

HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 228227Diallyl malonateHCID 128865484-(2-Bromoethyl)benzonitrileHCID 178418361HCID 178418361, compound

Product 1

HCID 57971936Diallyl 2-[2-(4-cyanophenyl)ethyl]malonate

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Procedure

5.59 g (139.88 mmol) of 60% pure sodium hydride are added in portions (caution: evolution of hydrogen) to a solution of 34.35 g (186.51 mmol) of diallyl malonate in 300 ml of dioxane at 0° C. The mixture is warmed to room temperature and then stirred at 40° C. for 30 minutes. Subsequently, at 40° C., 19.59 g (93.25 mol) of 4-(2-bromoethyl)benzonitrile, dissolved in 200 ml of dioxane, are slowly added dropwise, and the reaction solution is then stirred at 110° C. overnight. After cooling to room temperature, the reaction mixture is added to 200 ml of saturated ammonium chloride solution. 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 sulfate. After filtration, the solvent is concentrated 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: cyclohexane/ethyl acetate 9:1→4:1). 14.18 g (24% of theory) of a colorless solid are obtained.

Workup

  1. additionare slowly added dropwise
  2. stirringthe reaction solution is then 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 sulfate
  7. filtrationAfter filtration
  8. concentrationthe solvent is concentrated 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: cyclohexane/ethyl acetate 9:1→4:1)
  11. custom14.18 g (24% of theory) of a colorless solid are obtained

Sources & evidence

ORD record
ord-06f51420bb0e4c18816b4b79406f5c9b
Source dataset
uspto-grants-2012_05
Patent number
US08173704B2

Reaction notes

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