Water → Diallyl 2-(4-cyanobutyl)-2-[2-(4-methoxycarbonylphenyl)ethyl]malonate

HRID 1927423Notes

Reaction equation

HRID 1927423 reaction equation
[H-].[Na+].[C:3]([CH2:5][CH2:6][CH2:7][CH2:8][CH:9]([C:16]([O:18][CH2:19][CH:20]=[CH2:21])=[O:17])[C:10]([O:12][CH2:13][CH:14]=[CH2:15])=[O:11])#[N:4].Br[CH2:23][CH2:24][C:25]1[CH:34]=[CH:33][C:28]([C:29]([O:31][CH3:32])=[O:30])=[CH:27][CH:26]=1.O>CN(C=O)C>[C:3]([CH2:5][CH2:6][CH2:7][CH2:8][C:9]([CH2:23][CH2:24][C:25]1[CH:34]=[CH:33][C:28]([C:29]([O:31][CH3:32])=[O:30])=[CH:27][CH:26]=1)([C:10]([O:12][CH2:13][CH:14]=[CH2:15])=[O:11])[C:16]([O:18][CH2:19][CH:20]=[CH2:21])=[O:17])#[N:4]

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 10586287Methyl 4-(2-bromoethyl)benzoateHCID 57831342Diallyl 2-(4-cyanobutyl)malonate

Product 1

HCID 57831337Diallyl 2-(4-cyanobutyl)-2-[2-(4-methoxycarbonylphenyl)ethyl]malonate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

5.62 g (140 mmol; 60% pure) of sodium hydride are added in portions to a solution of 48.64 g (127.73 mmol) of diallyl 2-(4-cyanobutyl)malonate in 160 ml of dry DMF at 0° C. The reaction solution is then allowed to reach room temperature and is stirred for 90 min. The reaction solution is then cooled to 0° C. again and, after addition of 45.72 g (153.3 mmol) of methyl 4-(2-bromoethyl)benzoate in 80 ml of dry DMF, stirred at this temperature for 45 min. The mixture is then stirred at room temperature overnight. The reaction mixture is mixed with water and extracted with ethyl acetate. After phase separation, the aqueous phase is extracted three more times with 200 ml of ethyl acetate each time. After combining the combined organic phases, the mixture is washed with saturated sodium chloride solution and dried over sodium sulfate, and then the solvent is stripped off in vacuo. The resulting crude product is purified by silica gel chromatography (mobile phase: cyclohexane/ethyl acetate 10:1→100% ethyl acetate). 18.53 g (43.3 mmol, 34% of theory) of a colorless liquid are obtained.

Workup

  1. customto reach room temperature
  2. stirringstirred at this temperature for 45 min
  3. stirringThe mixture is then stirred at room temperature overnight
  4. extractionextracted with ethyl acetate
  5. customAfter phase separation
  6. extractionthe aqueous phase is extracted three more times with 200 ml of ethyl acetate each time
  7. washthe mixture is washed with saturated sodium chloride solution
  8. dry with materialdried over sodium sulfate
  9. customThe resulting crude product is purified by silica gel chromatography (mobile phase: cyclohexane/ethyl acetate 10:1→100% ethyl acetate)
  10. custom18.53 g (43.3 mmol, 34% of theory) of a colorless liquid are obtained

Sources & evidence

ORD record
ord-ba08b57dc7b243a18bbd33222b4d87dc
Source dataset
uspto-grants-2012_05
Patent number
US08183271B2

Reaction notes

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