N-bromobutanimide → 4-Bromo-3-(bromomethyl)benzonitrile

HRID 1867635Notes

Reaction equation

HRID 1867635 reaction equation
[Br:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[CH3:10].[Br:11]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.C(Cl)Cl>[Br:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[CH2:10][Br:11]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 27374944-Bromo-3-methylbenzonitrile

Product 1

HCID 114713444-Bromo-3-(bromomethyl)benzonitrileYield 61%

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 4-bromo-3-methyl benzonitrile (5 g, 25.5 mmol) in CCl4 (200 mL), was added N-bromosuccinimide (4.99 g, 28.05 mmol) and 2,2-Azobisisobutyronitrile (335 mg, 2.04 mmol). The mixture was heated to reflux overnight then cooled, diluted with CH2Cl2 and quenched with 10% NaHSO3. The layers were separated and the CH2Cl2 layer was washed with saturated NaHCO3 and brine, dried over MgSO4, filtered and concentrated under vacuum. Column chromatography on silica gel (5-10% ethyl acetate/hexanes) afforded 4.31 g (3.65 mmol, 61%) of a mixture of mono- and di-bromo intermediates. 1H NMR (400 MHz, CHLOROFORM-D) δ ppm 4.55 (s, 2H) 7.42 (dd, J=8.31, 2.01 Hz, 1H) 7.67-7.78 (m, 2H). Mass spec.: 275.94 (MH)+.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux overnight
  3. temperaturethen cooled
  4. customquenched with 10% NaHSO3
  5. customThe layers were separated
  6. washthe CH2Cl2 layer was washed with saturated NaHCO3 and brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-719ca8944c0e40a5a129460bed0143fc
Source dataset
uspto-grants-2009_12
Patent number
US07632861B2

Reaction notes

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