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

HRID 1672660Notes

Reaction equation

HRID 1672660 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].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: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:21][CH:22]=1)#[N:25]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 701274-(Chloromethyl)benzonitrileHCID 228227Diallyl malonateHCID 178418361HCID 178418361, compound

Product 1

HCID 57831332Diallyl 2-(4-cyanobenzyl)malonateYield 67%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent2×

Procedure

19.79 g (0.494 mol) of sodium hydride are added in portions (caution: evolution of hydrogen) to a solution of 121.5 g (0.659 mol) of diallyl malonate in 1.5 liters of dioxane at 0° C. The mixture is warmed to room temperature and then stirred at 40° C. for 1 hour. Subsequently, at 40° C., 50 g (0.329 mol) of 4-chloromethylbenzonitrile, dissolved in 500 ml of dioxane, are slowly added dropwise, 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 (where appropriate, a few ml of 1 M hydrochloric acid are metered in to about pH 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 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: petroleum ether/ethyl acetate 20:1). 67 g (0.22 mol, 67% yield) of a colorless solid are obtained.

Workup

  1. additionare slowly added dropwise
  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 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: petroleum ether/ethyl acetate 20:1)

Sources & evidence

ORD record
ord-9a60702c14934bd187a60b93fbc1b77f
Source dataset
uspto-grants-2011_08
Patent number
US07998988B2

Reaction notes

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