1,2-Dibromoethane → Methyl 3-(1-cyanocyclopropyl)benzoate

HRID 1800406Notes

Reaction equation

HRID 1800406 reaction equation
[C:1]([CH2:3][C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][CH:13]=1)[C:7]([O:9][CH3:10])=[O:8])#[N:2].[H-].[Na+].Br[CH2:17][CH2:18]Br>CS(C)=O.O>[C:1]([C:3]1([C:4]2[CH:5]=[C:6]([CH:11]=[CH:12][CH:13]=2)[C:7]([O:9][CH3:10])=[O:8])[CH2:18][CH2:17]1)#[N:2]

Participants

6

Reactant 3

HCID 78391,2-DibromoethaneHCID 24758Sodium hydrideHCID 10821136Methyl 3-(cyanomethyl)benzoate

Product 1

HCID 57441038Methyl 3-(1-cyanocyclopropyl)benzoateYield 76%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Procedure

To a solution of methyl 3-(cyanomethyl)benzoate (1.5 g, 8.6 mmol) produced in Example B2(viii) in dimethyl sulfoxide (30 mL) was added sodium hydride (60% in oil, 1.0 g, 26 mmol) while cooling the solution to a temperature of 25° C. or below at which the solution did not solidify. The reaction mixture was stirred at room temperature for 30 min, 1,2-dibromoethane (2.4 g, 12.8 mmol) was added, and the mixture was further stirred at room temperature for 10 hr. The reaction mixture was diluted with water (100 mL), and extracted with ethyl acetate (300 mL). The organic layer was washed with saturated brine (100 mL), and dried over anhydrous sodium sulfate, and the insoluble material was filtered off. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate/hexane=5/95→50/50). The combined solution was concentrated under reduced pressure to give the title compound (1.3 g, 76%) as a colorless oil.

Workup

  1. temperaturewhile cooling the solution to a temperature of 25° C. or below at which the solution
  2. stirringthe mixture was further stirred at room temperature for 10 hr
  3. extractionextracted with ethyl acetate (300 mL)
  4. washThe organic layer was washed with saturated brine (100 mL)
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationthe insoluble material was filtered off
  7. customThe solvent was evaporated under reduced pressure
  8. customthe residue was purified by silica gel column chromatography (ethyl acetate/hexane=5/95→50/50)
  9. concentrationThe combined solution was concentrated under reduced pressure

Sources & evidence

ORD record
ord-1b3e17d6310c479db6981d6cb18516a5
Source dataset
uspto-grants-2013_01
Patent number
US08344135B2

Reaction notes

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