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

HRID 1672661Notes

Reaction equation

HRID 1672661 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]malonateYield 44,634.301%

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 70A 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 to 0° C. again and, after addition of 55 g (194.57 mmol) of methyl 4-(2-bromoethyl)benzoate [CAS 136333-97-6] in 195 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, which 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. 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 mol, 44% yield) of a colorless solid are obtained.

Workup

  1. customto reach room temperature
  2. stirringstirred at this temperature for 30 min
  3. stirringThe mixture is then stirred at room temperature overnight
  4. extractionis 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. customThe resulting crude product is purified by flash chromatography on silica gel (mobile phase: petroleum ether/ethyl acetate 10:1)

Sources & evidence

ORD record
ord-8efe302fa58d44b58bac9d10bd48c139
Source dataset
uspto-grants-2011_08
Patent number
US07998988B2

Reaction notes

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