Azobisisobutyronitrile → 1-(Bromomethyl)-2-chloro-4-nitrobenzene

HRID 923225Notes

Reaction equation

HRID 923225 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH3:11].[Br:12]N1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C(Cl)(Cl)(Cl)Cl>[Br:12][CH2:11][C:3]1[CH:4]=[CH:5][C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]=1[Cl:1]

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 84912-Chloro-4-nitrotolueneHCID 67184N-bromobutanimide

Product 1

HCID 30163681-(Bromomethyl)-2-chloro-4-nitrobenzene

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A suspension of 2-chloro-4-nitrotoluene (10.0 g, 58.3 mmol), N-bromosuccinimide (NBS, 10.9 g, 61.2 mmol), and 2,2′-azobis(2-methylpropionitrile) (AIBN, 0.29 g, 1.75 mmol) in 120 mL of CCl4 was heated at reflux under an atmosphere of N2 for 12 h. The reaction mixture was cooled to ambient temperature, and the solid was filtered and washed with EtOAc. The combined filtrate was washed with aq. NaHCO3, dried over Na2SO4, filtered, concentrated on rotovap, and further dried under vacuum. 1H NMR indicated the ratio of desired product to unreacted 2-chloro-4-nitrotoluene to be 50:50. This material was used directly in the next step.

Workup

  1. temperaturewas heated
  2. temperatureat reflux under an atmosphere of N2 for 12 h
  3. filtrationthe solid was filtered
  4. washwashed with EtOAc
  5. washThe combined filtrate was washed with aq. NaHCO3
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated on rotovap
  9. customfurther dried under vacuum

Sources & evidence

ORD record
ord-88dafe97c2de46f3b7e354cb61f99150
Source dataset
uspto-grants-2016_03
Patent number
US09278971B2

Reaction notes

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