Azobisisobutyronitrile → HCID 16223016, compound

HRID 856986Notes

Reaction equation

HRID 856986 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:12]=[C:11]([C:13]3[S:14][CH:15]=[CH:16][C:17]=3[Cl:18])[O:10][N:9]=2)=[CH:4][C:3]=1[CH3:19].C1C(=O)N([Br:27])C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C.BrBr>C(Cl)(Cl)(Cl)Cl>[Br:27][CH2:19][C:3]1[CH:4]=[C:5]([C:8]2[N:12]=[C:11]([C:13]3[S:14][CH:15]=[CH:16][C:17]=3[Cl:18])[O:10][N:9]=2)[CH:6]=[CH:7][C:2]=1[Cl:1]

Participants

6

Reactant 4

HCID 6547Azobisisobutyronitrile2×HCID 24408BromineHCID 67184N-bromobutanimide2×HCID 16222808HCID 16222808, compound

Product 1

HCID 16223016HCID 16223016, compoundYield 44.4%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A solution of 3-(4-chloro-3-methyl-phenyl)-5-(3-chlorothiophen-2-yl)-[1,2,4]oxadiazole (1.45 g, 4.66 mmol), NBS (0.923 g, 5.19 mmol), AIBN (0.844 g, 5.14 mmol) and CCl4 (300 mL) was refluxed at 80° C. for 2 h. The solution was cooled to room temperature and additional NBS (0.913 g, 5.13 mmol) and AIBN (0.218 g, 1.33 mmol) was added and the solution was refluxed for 1 h. The solution was cooled to room temperature and stirred for 17 h. TLC indicated that the reaction had not occurred so bromine (0.240 mL, 4.67 mmol) was added and the solution was then brought to reflux. While refluxing, the solution was irradiated with a UV lamp (254 nm, 18.4 watts) for 2 h. The solution was cooled to room temperature, filtered and the solvent was removed by rotary evaporation. The residue was purified by flash column chromatography (silica gel, hexanes:dichloromethane, 8:3), to give 0.808 g (44%) of the title compound as a white solid. 1H NMR (CDCl3): 8.24 (d, 1H, J=2.2 Hz), 8.06 (dd, 1H, J=8.5 and 2.2 Hz), 7.63 (d, 1H, J=5.2 Hz), 7.54 (d, 1H, J=8.3 Hz), 7.14 (d, 1H, J=5.2 Hz), 4.66 (s, 2H).

Workup

  1. temperaturethe solution was refluxed for 1 h
  2. temperatureThe solution was cooled to room temperature
  3. additionwas added
  4. temperatureto reflux
  5. temperatureWhile refluxing
  6. customthe solution was irradiated with a UV lamp (254 nm, 18.4 watts) for 2 h
  7. temperatureThe solution was cooled to room temperature
  8. filtrationfiltered
  9. customthe solvent was removed by rotary evaporation
  10. customThe residue was purified by flash column chromatography (silica gel, hexanes:dichloromethane, 8:3)

Sources & evidence

ORD record
ord-d19570de0da9445c96a477f70f475305
Source dataset
uspto-grants-2006_12
Patent number
US07144876B2

Reaction notes

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