Pyridine → 6-bromo-2-(2-ethylsulfanylphenyl)-3-methyl-3H-imidazo[4,5-b]pyridine

HRID 923748Notes

Reaction equation

HRID 923748 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([NH2:10])[C:5]([NH:8][CH3:9])=[N:6][CH:7]=1.[CH2:11]([S:13][C:14]1[CH:22]=[CH:21][CH:20]=[CH:19][C:15]=1[C:16](O)=O)[CH3:12].CCN=C=NCCCN(C)C.N1C=CC=CC=1>C1C=CC2N(O)N=NC=2C=1.O>[Br:1][C:2]1[CH:3]=[C:4]2[N:10]=[C:16]([C:15]3[CH:19]=[CH:20][CH:21]=[CH:22][C:14]=3[S:13][CH2:11][CH3:12])[N:8]([CH3:9])[C:5]2=[N:6][CH:7]=1

Participants

7

Reactant 4

HCID 1049PyridineHCID 159081-Ethyl-3-(3'-dimethylaminopropyl)carbodiimideHCID 4257582-(Ethylsulfanyl)benzoic acidHCID 151940325-Bromo-N2-methylpyridine-2,3-diamine

Product 1

HCID 679820336-bromo-2-(2-ethylsulfanylphenyl)-3-methyl-3H-imidazo[4,5-b]pyridineYield 49.7%

Reagents, catalysts & solvents 2

HCID 757711-HydroxybenzotriazoleCatalystHCID 962WaterSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 5-bromo-N2-methylpyridin-2,3-diamine (0.70 g), 2-ethylsulfanylbenzoic acid (0.66 g), WSC (0.80 g), HOBt (23 mg), and pyridine (20 ml) was stirred under reflux at 120° C. for 30 minutes. After the reaction mixture was allowed to stand overnight, the mixture was stirred under reflux at 120° C. for 9.5 hours again. Into the reaction mixture cooled to room temperature, water was poured under ice-cooling, and extracted with ethyl acetate. The organic layer was washed with wafer and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. A mixture of the resulting residue and acetic anhydride (7 ml) was stirred under reflux at 140° C. for 1 hour. Aqueous sodium hydroxide solution was added to the reaction mixture cooled to room temperature to neutralize, and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 0.60 g of 6-bromo-2-(2-ethylsulfanylphenyl)-3-methyl-3H-imidazo[4,5-b]pyridine (hereinafter referred to as Present Compound 42).

Workup

  1. stirringthe mixture was stirred
  2. temperatureunder reflux at 120° C. for 9.5 hours again
  3. temperatureInto the reaction mixture cooled to room temperature
  4. temperaturecooling
  5. extractionextracted with ethyl acetate
  6. washThe organic layer was washed with wafer and saturated brine
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. additionA mixture of the resulting residue and acetic anhydride (7 ml)
  10. stirringwas stirred
  11. temperatureunder reflux at 140° C. for 1 hour
  12. additionAqueous sodium hydroxide solution was added to the reaction mixture
  13. temperaturecooled to room temperature
  14. extractionextracted with ethyl acetate
  15. washThe organic layer was washed with water and saturated brine
  16. dry with materialdried over sodium sulfate
  17. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-e00c9ca761784e689832749656be4dc4
Source dataset
uspto-grants-2016_03
Patent number
US09278983B2

Reaction notes

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