Cesium carbonate → HCID 58216913, compound

HRID 513140Notes

Reaction equation

HRID 513140 reaction equation
C(=O)([O-])[O-].[Cs+].[Cs+].Br[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[CH2:14][C:15]#[N:16].[CH3:17][C:18]1[CH:22]=[CH:21][NH:20][N:19]=1>[Cu](I)I>[CH3:17][C:18]1[CH:22]=[CH:21][N:20]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[CH2:14][C:15]#[N:16])[N:19]=1

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 296252-Bromobenzyl cyanideHCID 178428694HCID 178428694, compound

Product 1

HCID 58216913HCID 58216913, compound

Reagents, catalysts & solvents 1

HCID 83717Copper iodideCatalyst

Conditions

Temperature
120 °C

Procedure

A round bottom flask was charged under inert atmosphere with copper iodide (760 mg, 4 mmol), cesium carbonate (3.91 g, 12 mmol) then dimethylformamide (20 mL), previously degassed, was added followed by 2-Bromophenylacetonitrile (519 μL, 4 mmol), 3-Methylpyrazole (3.32 mL, 40 mmol) and N—N′-dimethylethylenediamine (425.86 μL, 4 mmol). The reaction mixture was heated to 120° C. for 2.5 hours. After cooling the reaction mixture was filtered through a Celite pad that was rinsed with dimethylformamide. The volume was reduced under reduced pressure, saturated ammonium chloride aqueous solution was added and extracted with ethyl acetate. The organic phase was washed with saturated aqueous NH4Cl solution, brine then dried over Na2SO4 and the solvent was removed under reduced pressure. The crude product was purified by flash chromatography on SiO2 using cyclohexane/ethyl acetate mixture of increasing polarity (from 100% cyclohexane to 100% ethyl acetate) as eluent. The oil obtained was further purified by SPE Stratosphere “PL-THIOL MP” to completely remove copper salts. The title compound was obtained as a thick dark oil (300 mg, 38%).

Workup

  1. customdimethylformamide (20 mL), previously degassed
  2. additionwas added
  3. temperatureAfter cooling the reaction mixture
  4. filtrationwas filtered through a Celite pad that
  5. washwas rinsed with dimethylformamide
  6. additionwas added
  7. extractionextracted with ethyl acetate
  8. washThe organic phase was washed with saturated aqueous NH4Cl solution, brine
  9. dry with materialthen dried over Na2SO4
  10. customthe solvent was removed under reduced pressure
  11. customThe crude product was purified by flash chromatography on SiO2
  12. additioncyclohexane/ethyl acetate mixture
  13. temperatureof increasing polarity (from 100% cyclohexane to 100% ethyl acetate) as eluent
  14. customThe oil obtained
  15. customwas further purified by SPE Stratosphere “PL-THIOL MP” to completely remove copper salts

Sources & evidence

ORD record
ord-237693969c01423cabf14d14b7800b03
Source dataset
uspto-grants-2015_08
Patent number
US09102679B2

Reaction notes

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