Azobisisobutyronitrile → 4-(azidomethyl)-1-(4-iodophenyl)-1H-pyrazole

HRID 643028Notes

Reaction equation

HRID 643028 reaction equation
[I:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH:12]=[C:11]([CH3:13])[CH:10]=[N:9]2)=[CH:4][CH:3]=1.C1C(=O)N(Br)C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C.[N-:34]=[N+:35]=[N-:36].[Na+]>C(Cl)(Cl)(Cl)Cl.CCOC(C)=O.O>[N:34]([CH2:13][C:11]1[CH:10]=[N:9][N:8]([C:5]2[CH:4]=[CH:3][C:2]([I:1])=[CH:7][CH:6]=2)[CH:12]=1)=[N+:35]=[N-:36]

Participants

8

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 33557Sodium AzideHCID 67184N-bromobutanimideHCID 685096071-(4-iodophenyl)-4-methyl-1H-pyrazole

Product 1

HCID 866140084-(azidomethyl)-1-(4-iodophenyl)-1H-pyrazoleYield 35.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 5943Carbon TetrachlorideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 1-(4-iodophenyl)-4-methyl-1H-pyrazole (1.70 g, 5.99 mmol), NBS (1.38 g, 7.75 mmol) and AIBN (0.30 g, 1.83 mmol) in CCl4 (25 mL) was heated at reflux for 1 hr. After being cooled to room temperature, the upper clear solution was decanted out and concentrated in vacuo. The residue was dissolved in DMF (10 mL), NaN3 (0.934 g, 14.3 mmol) was added. The mixture was stirred at room temperature overnight. H2O and EtOAc were added. The organic phase was separated, dried over Na2SO4, concentrated in vacuo. The residue was purified by a silica gel column, eluted with hexane, then with 5% EtOAc in hexane to give 4-(azidomethyl)-1-(4-iodophenyl)-1H-pyrazole (0.70 g).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 1 hr
  3. customthe upper clear solution was decanted out and
  4. concentrationconcentrated in vacuo
  5. dissolutionThe residue was dissolved in DMF (10 mL)
  6. customThe organic phase was separated
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by a silica gel column
  10. washeluted with hexane

Sources & evidence

ORD record
ord-fe1888e3a3de49fe905c175f850b07e2
Source dataset
uspto-grants-2010_04
Patent number
US07696352B2

Reaction notes

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