Water → 1-Allyl 7-ethyl 2-allyloxycarbonyl-2-(4-cyanobenzyl)heptanedioate

HRID 1927439Notes

Reaction equation

HRID 1927439 reaction equation
[H-].[Na+].[CH2:3]([O:6][C:7]([CH:9]([CH2:16][CH2:17][CH2:18][CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:10]([O:12][CH2:13][CH:14]=[CH2:15])=[O:11])=[O:8])[CH:4]=[CH2:5].Br[CH2:26][C:27]1[CH:34]=[CH:33][C:30]([C:31]#[N:32])=[CH:29][CH:28]=1.O>CN(C=O)C>[CH2:3]([O:6][C:7]([C:9]([CH2:26][C:27]1[CH:34]=[CH:33][C:30]([C:31]#[N:32])=[CH:29][CH:28]=1)([CH2:16][CH2:17][CH2:18][CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:10]([O:12][CH2:13][CH:14]=[CH2:15])=[O:11])=[O:8])[CH:4]=[CH2:5]

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 869964-(Bromomethyl)benzonitrileHCID 578313641-Allyl 7-ethyl 2-allyloxycarbonylheptanedioate

Product 1

HCID 578313451-Allyl 7-ethyl 2-allyloxycarbonyl-2-(4-cyanobenzyl)heptanedioate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

1.69 g (70.43 mmol) of sodium hydride are added in portions to a solution of 20 g (64.03 mmol) of 1-allyl 7-ethyl 2-allyloxycarbonylheptanedioate in 140 ml of DMF at 0° C. The reaction mixture is then allowed to reach room temperature and is stirred for 30 min. The reaction solution is cooled to 0° C. again and, after addition of 16.32 g (83.24 mmol) of 4-bromomethylbenzonitrile 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 an silica gel (mobile phase: cyclohexane/ethyl acetate 10:1→4:1→1:1). 20.08 g (46.97 mmol, 73% of theory) 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. 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 an silica gel (mobile phase: cyclohexane/ethyl acetate 10:1→4:1→1:1)
  10. custom20.08 g (46.97 mmol, 73% of theory) of a colorless solid are obtained

Sources & evidence

ORD record
ord-397fa7aa6dee41f4a992aa2c0ed072bb
Source dataset
uspto-grants-2012_05
Patent number
US08183271B2

Reaction notes

Loading…