Azobisisobutyronitrile → HCID 86654436, compound

HRID 1909904Notes

Reaction equation

HRID 1909904 reaction equation
[C:1]([C:5]1[N:6]([C:20]([OH:22])=[O:21])[C:7]2[C:12]([CH:13]=1)=[CH:11][C:10]([Br:14])=[C:9]([C:15]([F:18])([F:17])[F:16])[C:8]=2[CH3:19])([CH3:4])([CH3:3])[CH3:2].BrN1C(=[O:29])CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C(Cl)(Cl)(Cl)Cl>[C:1]([C:5]1[N:6]([C:20]([OH:22])=[O:21])[C:7]2[C:12]([CH:13]=1)=[CH:11][C:10]([Br:14])=[C:9]([C:15]([F:17])([F:18])[F:16])[C:8]=2[CH:19]=[O:29])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 66868373HCID 66868373, compound

Product 1

HCID 86654436HCID 86654436, compoundYield 20.9%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
90 °C

Procedure

To a mixture of tert-butyl 5-bromo-7-methyl-6-(trifluoromethyl)-1H-indole-1-carboxylic acid (1.2 g) and carbon tetrachloride (20 mL) were added N-bromosuccinimide (0.70 g) and 2,2′-azobis(2-methylpropionitrile) (20 mg) at room temperature. The reaction mixture was stirred at 90° C. for 18 hours. The reaction mixture was left to be cooled to room temperature and filtered through Celite to remove the insoluble materials. The filtrate was evaporated under reduced pressure, and to the residue was added acetonitrile (20 mL), followed by addition of 4-methyl morpholine-4-oxide (0.50 g) under ice-cooling. The reaction mixture was stirred at room temperature for 24 hours. The reaction mixture was evaporated under reduced pressure, ethyl acetate and water were added thereto, and a liquid-separation operation was carried out. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0-90:10) to obtain tert-butyl 5-bromo-7-formyl-6-(trifluoromethyl)-1H-indole-1-carboxylic acid (0.26 g).

Workup

  1. waitThe reaction mixture was left
  2. temperatureto be cooled to room temperature
  3. filtrationfiltered through Celite
  4. customto remove the insoluble materials
  5. customThe filtrate was evaporated under reduced pressure
  6. additionto the residue was added acetonitrile (20 mL)
  7. additionfollowed by addition of 4-methyl morpholine-4-oxide (0.50 g) under ice-
  8. temperaturecooling
  9. stirringThe reaction mixture was stirred at room temperature for 24 hours
  10. customThe reaction mixture was evaporated under reduced pressure, ethyl acetate and water
  11. additionwere added
  12. washThe organic layer was washed with saturated brine
  13. dry with materialdried over anhydrous sodium sulfate
  14. customevaporated under reduced pressure
  15. customThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=100:0-90:10)

Sources & evidence

ORD record
ord-4f0f2ae9bdd54c1aa1922c1e827df412
Source dataset
uspto-grants-2013_12
Patent number
US08598355B2

Reaction notes

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