N-bromobutanimide → 4-(Bromomethyl)-3-chlorobenzonitrile

HRID 1502855Notes

Reaction equation

HRID 1502855 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[CH3:10])[C:5]#[N:6].C1C(=O)N([Br:18])C(=O)C1>C(Cl)(Cl)(Cl)Cl.N(C(C)(C)C#N)=NC(C)(C)C#N>[Br:18][CH2:10][C:9]1[CH:8]=[CH:7][C:4]([C:5]#[N:6])=[CH:3][C:2]=1[Cl:1]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 888943-Chloro-p-toluonitrile

Product 1

HCID 130420934-(Bromomethyl)-3-chlorobenzonitrileYield 82%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

To a stirred solution of 3-chloro-4-methylbenzonitrile (5 g, 25.4 mmol) in carbon tetrachloride (CCl4; 50 mL) under an argon atmosphere was added NBS (5.16 g, 29 mmol), and the mixture was degassed for 30 min. To this was added azobisisobutyronitrile (AIBN; 0.3 g, 1.8 mmol), and the resultant reaction mixture was heated at reflux for 4 h. The reaction mixture was cooled to ambient temperature, washed with water, and extracted with CH2Cl2. The combined CH2Cl2 layer was washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude compound was purified by flash column chromatography (SiO2, 100-200 mesh; 5% EtOAc in n-Hexane) to afford the title compound as a white solid (4.8 g, 68%): mp 87-88° C.; 1H NMR (400 MHz, CDCl3) δ 7.71 (s, 1H), 7.59 (s, 2H), 4.60 (s, 2H); ESIMS m/z 229.77 ([M+H]+); IR (thin film) 2235, 752, 621 cm−1.

Workup

  1. customthe mixture was degassed for 30 min
  2. customthe resultant reaction mixture
  3. temperaturewas heated
  4. temperatureat reflux for 4 h
  5. washwashed with water
  6. extractionextracted with CH2Cl2
  7. washThe combined CH2Cl2 layer was washed with brine
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated under reduced pressure
  10. customThe crude compound was purified by flash column chromatography (SiO2, 100-200 mesh; 5% EtOAc in n-Hexane)

Sources & evidence

ORD record
ord-25b5ba682e234186b6ebb47bd2205eb0
Source dataset
uspto-grants-2015_12
Patent number
US09211280B2

Reaction notes

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