Potassium Carbonate → 5-((4-Bromo-3-methylphenyl)sulfonyl)-2-pyridinamine

HRID 1972689Notes

Reaction equation

HRID 1972689 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([O-:10])=[O:9])=[CH:4][C:3]=1[CH3:11].[Na+].[NH2:13][C:14]1[CH:19]=[CH:18][C:17](I)=[CH:16][N:15]=1.C(=O)([O-])[O-].[K+].[K+].CN(C)CCN>[Cu](I)I.CS(C)=O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([C:17]2[CH:18]=[CH:19][C:14]([NH2:13])=[N:15][CH:16]=2)(=[O:10])=[O:9])=[CH:4][C:3]=1[CH3:11]

Participants

7

Reactant 4

HCID 11430Potassium CarbonateHCID 66053N,N-DimethylethylenediamineHCID 885792-Pyridinamine, 5-iodo-HCID 23712900Sodium 4-bromo-3-methylbenzenesulfinate

Product 1

HCID 665825595-((4-Bromo-3-methylphenyl)sulfonyl)-2-pyridinamineYield 20.3%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
100 °C

Procedure

Sodium 4-bromo-3-methylbenzenesulfinate (2.92 mg, 11.36 mmol), 2-amino-5-iodopyridine (1.25 g, 5.68 mmol, Alfa Aesar, Ward Hill, Mass.), copper iodide (216 mg, 1.14 mmol, Strem Chemical Inc, Newburyport, Mass.), potassium carbonate (785 mg, 5.68 mmol), N,N-dimethylethylenediamine (0.25 mL, 2.27 mmol, Alfa Aesar, Ward Hill, Mass.), and DMSO (15 mL) were added to a reaction vial. The vial was closed, purged with nitrogen for several minutes, and heated at 100° C. for 16 h. After cooling to room temperature, the reaction mixture was diluted with water (20 mL) and extracted with EtOAc (20 mL×3). The combined organic extracts were dried over Na2SO4. The solution was filtered and concentrated in vacuo to give the crude material. The crude material was absorbed onto a plug of silica gel and purified by chromatography through a Redi-Sep pre-packed silica gel column (40 g), eluting with a gradient of 20% to 50% EtOAc in hexane, to provide 5-((4-bromo-3-methylphenyl)sulfonyl)-2-pyridinamine (377 mg) as a white solid.

Workup

  1. customThe vial was closed
  2. custompurged with nitrogen for several minutes
  3. temperatureAfter cooling to room temperature
  4. additionthe reaction mixture was diluted with water (20 mL)
  5. extractionextracted with EtOAc (20 mL×3)
  6. dry with materialThe combined organic extracts were dried over Na2SO4
  7. filtrationThe solution was filtered
  8. concentrationconcentrated in vacuo
  9. customto give the crude material
  10. customThe crude material was absorbed onto a plug of silica gel
  11. custompurified by chromatography through a Redi-Sep pre-packed silica gel column (40 g)
  12. washeluting with a gradient of 20% to 50% EtOAc in hexane

Sources & evidence

ORD record
ord-40091d83c8fc4ca3b1e4fa00b22941d0
Source dataset
uspto-grants-2013_04
Patent number
US08431563B2

Reaction notes

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