Ammonia → 3-Bromo-5-methylbenzonitrile

HRID 1770904Notes

Reaction equation

HRID 1770904 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[C:4]([Br:9])[CH:3]=1.[Cu](C#N)[C:11]#[N:12].N1C=CC=CC=1.N>O.CN(C=O)C>[Br:9][C:4]1[CH:3]=[C:2]([CH:7]=[C:6]([CH3:8])[CH:5]=1)[C:11]#[N:12]

Participants

7

Reactant 4

HCID 222AmmoniaHCID 1049PyridineHCID 153613,5-DibromotolueneHCID 178418260HCID 178418260, compound

Product 1

HCID 145678583-Bromo-5-methylbenzonitrileYield 147.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
190 °C

Procedure

A mixture of 1,3-dibromo-5-methylbenzene (1.0 g, 4.0 mmol), copper cyanide (0.179 g, 2.00 mmol), pyridine (0.323 mL, 4.00 mmol), and DMF (15 mL) were heated at 190° C. for 10 h in microwave reactor. The reaction mixture was allowed to cool to r.t., and then poured into a solution of H2O (20 mL) and aq. NH3 solution (25-35% NH3, 10 mL) and the water phase was extracted with EtOAc. The combined organic extracts were dried (Mg2SO4), filtered and concentrated in vacuo. The residue was purified by silica gel chromatography (hexane/EtOAc gradient elution) to afford the title compound (0.58 g, 74% yield): 1H NMR (500 MHz, CDCl3) δ ppm 2.39 (s, 3H) 7.41 (s, 1H) 7.58 (s, 1H) 7.60 (s, 1H); MS (EI) m/z 195 M+.

Workup

  1. temperatureto cool to r.t.
  2. extractionthe water phase was extracted with EtOAc
  3. dry with materialThe combined organic extracts were dried (Mg2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by silica gel chromatography (hexane/EtOAc gradient elution)

Sources & evidence

ORD record
ord-2a32029391da41cab27be07d8b5a41a9
Source dataset
uspto-grants-2016_02
Patent number
US09248129B2

Reaction notes

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