Sodium hydride → Diallyl {2-[4-(tert-butoxycarbonyl)phenyl]ethyl}[4-(methoxycarbonyl)benzyl]malonate

HRID 1913773Notes

Reaction equation

HRID 1913773 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[CH2:28][CH2:29][C:30]1[CH:42]=[CH:41][C:33]([C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35])=[CH:32][CH:31]=1>CN(C=O)C>[C:37]([O:36][C:34]([C:33]1[CH:41]=[CH:42][C:30]([CH2:29][CH2:28][C:12]([CH2:11][C:10]2[CH:9]=[CH:8][C:7]([C:5]([O:4][CH3:3])=[O:6])=[CH:26][CH:25]=2)([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:31][CH:32]=1)=[O:35])([CH3:40])([CH3:39])[CH3:38]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 10803033Tert-butyl 4-(2-bromoethyl)benzoateHCID 57831347Diallyl [4-(methoxycarbonyl)benzyl]malonate

Product 1

HCID 59180509Diallyl {2-[4-(tert-butoxycarbonyl)phenyl]ethyl}[4-(methoxycarbonyl)benzyl]malonateYield 14%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

0.6 g (14.92 mmol) of sodium hydride is added in portions to a solution of 4.13 g (12.43 mmol) of diallyl 2-(4-methoxycarbonylbenzyl)malonate in 40 ml of DMF at 0° C. The reaction solution is then allowed to reach room temperature and is stirred for 1 hour. The reaction solution is then cooled again to 0° C., 3.9 g (13.68 mmol) of tert-butyl 4-(2-bromoethyl)benzoate in 10 ml of DMF are added, and the mixture is stirred at this temperature for 30 min. The mixture is then stirred at room temperature overnight. The reaction mixture is added to ice-water and 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, and the resulting crude product is purified by preparative HPLC. 933 mg (1.7 mmol, 14% yield) 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 then stirred at room temperature overnight
  4. extractionextracted 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 preparative HPLC

Sources & evidence

ORD record
ord-43df0a9c2e1c4c0e8e795bf32fac45ed
Source dataset
uspto-grants-2013_12
Patent number
US08609727B2

Reaction notes

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