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

HRID 1913782Notes

Reaction equation

HRID 1913782 reaction equation
[H-].[Na+].[C:3]([C:5]1[CH:24]=[CH:23][C:8]([CH2:9][CH:10]([C:17]([O:19][CH2:20][CH:21]=[CH2:22])=[O:18])[C:11]([O:13][CH2:14][CH:15]=[CH2:16])=[O:12])=[CH:7][CH:6]=1)#[N:4].Br[CH2:26][CH2:27][C:28]1[CH:37]=[CH:36][C:31]([C:32]([O:34][CH3:35])=[O:33])=[CH:30][CH:29]=1.O>CN(C=O)C>[C:3]([C:5]1[CH:6]=[CH:7][C:8]([CH2:9][C:10]([CH2:26][CH2:27][C:28]2[CH:37]=[CH:36][C:31]([C:32]([O:34][CH3:35])=[O:33])=[CH:30][CH:29]=2)([C:11]([O:13][CH2:14][CH:15]=[CH2:16])=[O:12])[C:17]([O:19][CH2:20][CH:21]=[CH2:22])=[O:18])=[CH:23][CH:24]=1)#[N:4]

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 10586287Methyl 4-(2-bromoethyl)benzoateHCID 57831332Diallyl 2-(4-cyanobenzyl)malonate

Product 1

HCID 57831378Diallyl 2-(4-cyanobenzyl)-2-[2-(4-methoxycarbonylphenyl)ethyl]malonate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

7.13 g (178.36 mmol) of sodium hydride are added in portions to a solution of 48.53 g (162.14 mmol) of diallyl 2-(4-cyanobenzyl)malonate from Example 45A in 180 ml of DMF at 0° C. The reaction solution is then allowed to reach room temperature and is stirred for 30 min. The reaction solution is then cooled again to 0° C., 55 g (194.57 mmol) of methyl 4-(2-bromoethyl)benzoate [CAS Reg. No. 136333-97-6] in 195 ml of DMF are added, and the mixture is stirred at this temperature for 30 min. The mixture is subsequently stirred at room temperature overnight. Water is added dropwise to the reaction mixture, which is then extracted three times with ethyl acetate, and the combined organic phases are washed with saturated brine and dried over sodium sulphate. After filtration, the solvent is evaporated to dryness in vacuo. The resulting crude product is purified by flash chromatography on silica gel (mobile phase: petroleum ether/ethyl acetate 10:1). 33.4 g (72.37 mmol, 44% of theory) of a colourless solid are obtained.

Workup

  1. customto reach room temperature
  2. stirringthe mixture is stirred at this temperature for 30 min
  3. stirringThe mixture is subsequently stirred at room temperature overnight
  4. extractionis then extracted three times with ethyl acetate
  5. washthe combined organic phases are washed with saturated brine
  6. dry with materialdried over sodium sulphate
  7. filtrationAfter filtration
  8. customthe solvent is evaporated to dryness in vacuo
  9. customThe resulting crude product is purified by flash chromatography on silica gel (mobile phase: petroleum ether/ethyl acetate 10:1)
  10. custom33.4 g (72.37 mmol, 44% of theory) of a colourless solid are obtained

Sources & evidence

ORD record
ord-88897e8fe9d84d74847bce8c30a430ea
Source dataset
uspto-grants-2013_12
Patent number
US08609727B2

Reaction notes

Loading…