Azobisisobutyronitrile → HCID 83909193, compound

HRID 30625Notes

Reaction equation

HRID 30625 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]=[N:10][S:11][C:12]=2[CH3:13])=[CH:4][CH:3]=1.BrN1C(=[O:20])CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C(Cl)(Cl)(Cl)Cl>[F:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[N:9]=[N:10][S:11][C:12]=2[CH:13]=[O:20])=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 69206034HCID 69206034, compound

Product 1

HCID 83909193HCID 83909193, compoundYield 5.4%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A mixture of 4-(4-fluorophenyl)-5-methyl-1,2,3-thiadiazole (6.19 g), N-bromosuccinimide (12.4 g), 2,2′-azobis(isobutyronitrile) (100 mg) and carbon tetrachloride (100 ml) was stirred for 6 hrs. with heating under reflux. The reaction mixture was washed with water, dried over anhydrous magnesium sulfate and concentrated. Sodium acetate (30 g) and acetic acid (100 ml) were added to the residue and the mixture was stirred for 12 hrs. with heating under reflux. 6N Hydrochloric acid (50 ml) was added and the mixture was further stirred for 1 hr. with heating under reflux. The reaction mixture was concentrated, poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 4-(4-fluorophenyl)-1,2,3-thiadiazole-5-carbaldehyde (360 mg, yield 5.4%) as pale-yellow crystals from a fraction eluted with hexane-ethyl acetate (2:1, v/v).

Workup

  1. temperaturewith heating
  2. temperatureunder reflux
  3. washThe reaction mixture was washed with water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated
  6. additionSodium acetate (30 g) and acetic acid (100 ml) were added to the residue
  7. stirringthe mixture was stirred for 12 hrs
  8. temperaturewith heating
  9. temperatureunder reflux
  10. addition6N Hydrochloric acid (50 ml) was added
  11. stirringthe mixture was further stirred for 1 hr
  12. temperaturewith heating
  13. temperatureunder reflux
  14. concentrationThe reaction mixture was concentrated
  15. additionpoured into a saturated aqueous sodium hydrogen carbonate solution
  16. extractionextracted with ethyl acetate
  17. washThe organic layer was washed with saturated brine
  18. dry with materialdried over anhydrous magnesium sulfate
  19. concentrationconcentrated

Sources & evidence

ORD record
ord-a885b8f39e714bc7a8b6518185778091
Source dataset
uspto-grants-2008_09
Patent number
US07423159B2

Reaction notes

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