Azobisisobutyronitrile → 3-(azidomethyl)-1-(4-iodophenyl)-1H-pyrazole

HRID 643035Notes

Reaction equation

HRID 643035 reaction equation
[I:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH:12]=[CH:11][C:10]([CH3:13])=[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:10]1[CH:11]=[CH:12][N:8]([C:5]2[CH:4]=[CH:3][C:2]([I:1])=[CH:7][CH:6]=2)[N:9]=1)=[N+:35]=[N-:36]

Participants

8

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 33557Sodium AzideHCID 67184N-bromobutanimideHCID 685095051-(4-iodophenyl)-3-methyl-1H-pyrazole

Product 1

HCID 866140093-(azidomethyl)-1-(4-iodophenyl)-1H-pyrazoleYield 8.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 5943Carbon TetrachlorideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 1-(4-iodophenyl)-3-methyl-1H-pyrazole (0.98 g, 3.45 mmol), NBS (0.80 g, 4.49 mmol) and AIBN (0.17 g, 1.03 mmol) in CCl4 (15 mL) was heated at reflux for 5 hrs. After being cooled to room temperature, it was filtered. The filtrate was concentrated in vacuo. The residue was dissolved in DMF (8 mL), NaN3 (0.400 g, 6.15 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 4-6% EtOAc in hexane to give 3-(azidomethyl)-1-(4-iodophenyl)-1H-pyrazole (0.10 g).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 5 hrs
  3. filtrationit was filtered
  4. concentrationThe filtrate was concentrated in vacuo
  5. dissolutionThe residue was dissolved in DMF (8 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-64a06ee1185b44a18ff5b4e5cce2e831
Source dataset
uspto-grants-2010_04
Patent number
US07696352B2

Reaction notes

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