Potassium Carbonate → HCID 21099447, compound

HRID 2376949Notes

Reaction equation

HRID 2376949 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5](S)=[CH:4][CH:3]=1.Cl[C:10]1[CH:15]=[CH:14][C:13]([I:16])=[CH:12][N:11]=1.C(=O)([O-])[O-].[K+].[K+].FC1C=CC(SC2C=CC(I)=CN=2)=CC=1.O[O:39][S:40]([O-:42])=O.[K+].C(=O)([O-])O.[Na+]>C(#N)C.O.CO>[F:1][C:2]1[CH:7]=[CH:6][C:5]([S:40]([C:10]2[CH:15]=[CH:14][C:13]([I:16])=[CH:12][N:11]=2)(=[O:42])=[O:39])=[CH:4][CH:3]=1

Participants

10

Reactant 6

HCID 11430Potassium CarbonateHCID 677894-FluorothiophenolHCID 516892Sodium BicarbonateHCID 43971762-Chloro-5-iodopyridine2×HCID 21099450HCID 21099450, compoundHCID 23707502Potassium hydroxy sulfite2×

Product 1

HCID 21099447HCID 21099447, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

4-fluorobenzenethiol (0.32 g, 2.5 mmol) was taken up in acetonitrile (15 mL) and degassed for 15 minutes. 2-Chloro-5-iodopyridine (0.6 g, 2.51 mmol) and potassium carbonate (0.52 g, 3.76 mmol) were added and the reaction heated to reflux for 18 hours. The cooled reaction mixture was diluted with water and extracted with ethyl acetate (×2). The combined organic layers were washed with brine, dried over MgSO4 and concentrated in vacuo while loading onto silica. Dry flash column chromatography using isohexane-2% ethyl acetate/isohexane gave a 3:1 mixture of 2-[(4-fluorophenyl)thio]-5-iodopyridine:2-chloro-5-iodopyridine (0.7 g). This was taken up in methanol (10 mL) and treated portionwise with OXONE® (1.04 g, 1.69 mmol). The suspension was stirred at room temperature for 5 days. A further portion of OXONE® (0.51 g) was added and stirring continued overnight. Saturated sodium hydrogencarbonate solution was added and the suspension stirred for 45 minutes before being extracted with ethyl acetate (×2). The combined organic layers were washed with brine, dried over MgSO4 and concentrated in vacuo while loading onto silica. Dry flash column chromatography using 5-15% ethyl acetate/isohexane gave 2-[(4-fluorophenyl)sulfonyl]-5-iodopyridine (0.17 g), a 3.6:1 mixture of 2-[(4-fluorophenyl)sulfonyl]-5-iodopyridine:2-[(4-fluorophenyl)sulfinyl]-5-iodopyridine (0.2 g) and a 1.15:1 mixture of 2-[(4-fluorophenyl)sulfinyl]-5-iodopyridine:2-[(4-fluorophenyl)sulfonyl]-5-iodo-pyridine (0.14 g).

Workup

  1. customdegassed for 15 minutes
  2. temperaturethe reaction heated
  3. temperatureto reflux for 18 hours
  4. customThe cooled reaction mixture
  5. extractionextracted with ethyl acetate (×2)
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated in vacuo
  9. customDry flash column chromatography
  10. customgave
  11. stirringstirring continued overnight
  12. stirringthe suspension stirred for 45 minutes
  13. extractionbefore being extracted with ethyl acetate (×2)
  14. washThe combined organic layers were washed with brine
  15. dry with materialdried over MgSO4
  16. concentrationconcentrated in vacuo
  17. customDry flash column chromatography

Sources & evidence

ORD record
ord-fc4878b82d2848ed8a433cd584b92178
Source dataset
uspto-grants-2008_12
Patent number
US07468393B2

Reaction notes

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