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

HRID 2190358Notes

Reaction equation

HRID 2190358 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) in dimethyl sulfoxide (30 mL) was added sodium hydride (60% in oil, 1.0 g, 26 mmol) while cooling to not more than 25° C. without causing solidification. 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), and the fraction containing the object product was concentrated under reduced pressure to give the title compound (1.3 g, 76%) as a colorless oil.

Workup

  1. temperaturewhile cooling to not more than 25° C.
  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. additionthe fraction containing the object product
  10. concentrationwas concentrated under reduced pressure

Sources & evidence

ORD record
ord-2b96b273e9ea4607967f9a1a7005608e
Source dataset
uspto-grants-2012_12
Patent number
US08324395B2

Reaction notes

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