Water → Diallyl 2-(4-cyanobutyl)-2-(4-methoxycarbonylbenzyl)malonate

HRID 1672698Notes

Reaction equation

HRID 1672698 reaction equation
[H-].[Na+].[CH3:3][O:4][C:5]([C:7]1[CH:26]=[CH:25][C:10]([CH2:11][CH:12]([C:19]([O:21][CH2:22][CH:23]=[CH2:24])=[O:20])[C:13]([O:15][CH2:16][CH:17]=[CH2:18])=[O:14])=[CH:9][CH:8]=1)=[O:6].Br[CH:28]([CH2:31][CH2:32][CH3:33])[C:29]#[N:30].O>CN(C=O)C>[C:29]([CH2:28][CH2:31][CH2:32][CH2:33][C:12]([CH2:11][C:10]1[CH:9]=[CH:8][C:7]([C:5]([O:4][CH3:3])=[O:6])=[CH:26][CH:25]=1)([C:19]([O:21][CH2:22][CH:23]=[CH2:24])=[O:20])[C:13]([O:15][CH2:16][CH:17]=[CH2:18])=[O:14])#[N:30]

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 124706452-BromopentanenitrileHCID 57831347Diallyl [4-(methoxycarbonyl)benzyl]malonate

Product 1

HCID 57864376Diallyl 2-(4-cyanobutyl)-2-(4-methoxycarbonylbenzyl)malonateYield 62.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
40 °C

Procedure

1.88 g (78.23 mmol) of sodium hydride are added in portions to a solution of 20 g (60.18 mmol) of diallyl 2-(4-methoxycarbonylbenzyl)malonate from Example 12A in 140 ml of DMF at 0° C. The reaction solution is then warmed to 40° C. and is stirred at this temperature for 30 min. The reaction solution is then cooled to 0° C. again and, after addition of 10.73 g (66.20 mmol) of bromovaleronitrile in 140 ml of DMF, stirred at this temperature for 30 min. The mixture is then stirred at room temperature overnight. Water is added dropwise to the reaction mixture and, after extraction three times with ethyl acetate, 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. The resulting crude product is purified by flash chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 9:1→4:1). 15.5 g (37.49 mmol, 62% yield) of a colorless solid are obtained.

Workup

  1. temperatureThe reaction solution is then cooled to 0° C. again
  2. stirringstirred at this temperature for 30 min
  3. stirringThe mixture is then stirred at room temperature overnight
  4. extractionafter extraction 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. customThe resulting crude product is purified by flash chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 9:1→4:1)

Sources & evidence

ORD record
ord-a7f9db48c0d748678a6bbdbecf88d498
Source dataset
uspto-grants-2011_08
Patent number
US07998988B2

Reaction notes

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