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

HRID 2190505Notes

Reaction equation

HRID 2190505 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 C2(i) in dimethyl sulfoxide (30 mL) was added sodium hydride (60% in oil, 1.0 g, 26 mmol) under cooling to not more than 25° C. without causing solidification. The reaction mixture was stirred at room temperature for 30 min. After stirring, 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, 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. temperatureunder cooling to not more than 25° C.
  2. stirringAfter stirring
  3. stirringthe mixture was further stirred at room temperature for 10 hr
  4. extractionextracted with ethyl acetate (300 mL)
  5. washThe organic layer was washed with saturated brine (100 mL)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationthe insoluble material was filtered off
  8. customThe solvent was evaporated under reduced pressure
  9. customthe residue was purified by silica gel column chromatography (ethyl acetate/hexane=5/95→50/50)
  10. additionthe fraction containing the object product
  11. concentrationwas concentrated under reduced pressure

Sources & evidence

ORD record
ord-af783af77ad3426f8d91a460aed32543
Source dataset
uspto-grants-2012_12
Patent number
US08324395B2

Reaction notes

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