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

HRID 1874572Notes

Reaction equation

HRID 1874572 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 DMSO (30 mL) was added sodium hydride (60% in oil, 1.0 g, 26 mmol) while cooling the mixture to 25° C. or below to prevent precipitation. The reaction mixture was stirred at room temperature for 30 min, 1,2-dibromoethane (2.4 g, 12.8 mmol) was added thereto, 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 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 fractions containing the desired product were concentrated under reduced pressure to give the title compound (1.3 g, 76%) as a colorless oil.

Workup

  1. temperaturewhile cooling the mixture to 25° C. or below
  2. customprecipitation
  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, and insoluble material
  7. filtrationwas 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), and fractions
  10. additioncontaining the desired product
  11. concentrationwere concentrated under reduced pressure

Sources & evidence

ORD record
ord-092fe443a2d74c6493a932f8125a892f
Source dataset
uspto-grants-2012_11
Patent number
US08304557B2

Reaction notes

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