Phosphorus pentachloride → (4-Pyridylmethyl)sulfonyl chloride triflate

HRID 1709953Notes

Reaction equation

HRID 1709953 reaction equation
[F:1][C:2]([F:8])([F:7])[S:3]([OH:6])(=[O:5])=[O:4].[N:9]1[CH:14]=[CH:13][C:12]([CH2:15][S:16]([OH:19])(=O)=[O:17])=[CH:11][CH:10]=1.N1C=CC=CC=1CS(O)(=O)=O.P(Cl)(Cl)(Cl)(Cl)[Cl:32]>P(Cl)(Cl)(Cl)=O>[OH:6][S:3]([C:2]([F:8])([F:7])[F:1])(=[O:5])=[O:4].[N:9]1[CH:14]=[CH:13][C:12]([CH2:15][S:16]([Cl:32])(=[O:19])=[O:17])=[CH:11][CH:10]=1

Participants

6

Reactant 4

HCID 24819Phosphorus pentachlorideHCID 62406Trifluoromethanesulfonic acidHCID 14851064(Pyridin-4-yl)methanesulfonic acidHCID 190757172-Pyridinemethanesulfonic acid

Product 1

HCID 14851081(4-Pyridylmethyl)sulfonyl chloride triflateYield 84%

Reagents, catalysts & solvents 1

HCID 24813Phosphorus oxychlorideSolvent

Procedure

Trifluoromethanesulfonic acid (100 g, 0.67 mol) was rapidly added to a suspension of 4-pyridylmethanesulfonic acid (103 g, 0.6 mol) in phosphorous oxychloride (300 ml). The pyridylmethanesulfonic acid dissolved and reprecipitated as the triflate salt. The resulting suspension was cooled in ice for 30 min, then treated with phosphorous pentachloride (139 g, 0.67 mol) in Portions during 10 minutes. The mixture was allowed to warm to room temperature over 30 min and was then cautiously heated to reflux over a period of 1.5 hrs during which time extensive gas evolution occurred. After refluxing for 1 hr, the excess phosphorous oxychloride was distilled off under vacuum while maintaining the pot temperature below 80° C. The residual solid was dissolved in acetonitrile (200 ml), filtered and crystallized by the gradual addition of ether (400 ml). The product was recovered by filtration and washed with ether to afford a white solid (170 g, 84%).

Workup

  1. customreprecipitated as the triflate salt
  2. temperatureThe resulting suspension was cooled in ice for 30 min
  3. temperaturewas then cautiously heated
  4. temperatureto reflux over a period of 1.5 hrs during which time extensive gas evolution
  5. temperatureAfter refluxing for 1 hr
  6. distillationthe excess phosphorous oxychloride was distilled off under vacuum
  7. temperaturewhile maintaining the pot temperature below 80° C
  8. dissolutionThe residual solid was dissolved in acetonitrile (200 ml)
  9. filtrationfiltered
  10. customcrystallized by the gradual addition of ether (400 ml)
  11. filtrationThe product was recovered by filtration
  12. washwashed with ether

Sources & evidence

ORD record
ord-fe11be2ec2d14e8bace658c441b181aa
Source dataset
uspto-grants-1990_08
Patent number
US04952397

Reaction notes

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