Dimethyl Sulfoxide → HCID 22727961, compound

HRID 2086083Notes

Reaction equation

HRID 2086083 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([N+:9]([O-])=O)[C:5](Cl)=[N:6][CH:7]=1.[CH3:12][O:13][C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([NH2:20])[CH:15]=1.O.O.O.O.O.O.O.O.O.[S-2].[Na+].[Na+].[Cl-].[NH4+].[CH3:35]S(C)=O>CO>[Br:1][C:2]1[CH:3]=[C:4]2[N:9]=[CH:35][N:20]([C:16]3[CH:17]=[CH:18][CH:19]=[C:14]([O:13][CH3:12])[CH:15]=3)[C:5]2=[N:6][CH:7]=1

Participants

7

Reactant 5

HCID 679Dimethyl SulfoxideHCID 108243-MethoxyanilineHCID 25517Ammonium ChlorideHCID 73972Sodium sulfide nonahydrateHCID 70194125-Bromo-2-chloro-3-nitropyridine

Product 1

HCID 22727961HCID 22727961, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 5-bromo-2-chloro-3-nitropyridine (2.37 g, 10 mmol) and m-anisidine (1.34 ml, 12 mmol) in dimethylsulphoxide (7 ml) and triethylanine (7 ml, 50 mmol) was heated at 80° C. for 3 hours. The reaction was cooled to ambient temperature then partitioned between dichloromethane and water. The organic layer was washed with water, brine, dried over anhydrous sodium sulphate, filtered and evaporated to dryness to afford a red solid. This solid was suspended in methanol (100 ml) and treated with sodium sulphide nonahydrate (9.6 g, 40 mmol) and ammonium chloride (2.14 g, 40 mmol) then heated at reflux for 3 hours. The reaction was cooled, filtered and evaporated to dryness. The resulting orange residue was suspended in 98% formic acid (40 ml) and heated at 85° C. for 12 hours. The reaction was cooled, poured into water, neutralised with 2N sodium hydroxide and the solid extracted into ethyl acetate. The organics were washed with water, brine, dried over anhydrous sodium sulphate, filtered through a pad of silica and concentrated. Trituration of the residue with 25% ether in isohexane afforded 6-bromo-3-(3-methoxyphenyl)-3H-imidazo[4,5-b]pyridine as a pale yellow solid (3.04 g, 99% over 3 steps); δH (400 MHz, CDCl3) 3.89 (3H, s), 7.00 (1H, dd, J 8 and 2), 7.26-7.32 (2H, m), 7.48 (1H, t, J 8), 8.29 (2H, dd, J 12 and 2), 8.50 (1H, d, J 2); m/z (ES+) 304 and 306 (M++H).

Workup

  1. temperatureThe reaction was cooled to ambient temperature
  2. customthen partitioned between dichloromethane and water
  3. washThe organic layer was washed with water, brine
  4. dry with materialdried over anhydrous sodium sulphate
  5. filtrationfiltered
  6. customevaporated to dryness
  7. customto afford a red solid
  8. temperaturethen heated
  9. temperatureat reflux for 3 hours
  10. temperatureThe reaction was cooled
  11. filtrationfiltered
  12. customevaporated to dryness
  13. temperatureheated at 85° C. for 12 hours
  14. temperatureThe reaction was cooled
  15. additionpoured into water
  16. extractionthe solid extracted into ethyl acetate
  17. washThe organics were washed with water, brine
  18. dry with materialdried over anhydrous sodium sulphate
  19. filtrationfiltered through a pad of silica
  20. concentrationconcentrated

Sources & evidence

ORD record
ord-72c8bece07b4440cb09952ed9a8f1a47
Source dataset
uspto-grants-2004_04
Patent number
US06723735B1

Reaction notes

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