Sulfuryl chloride → 5-Pyridin-4-yl-thiophene-2-sulfonyl chloride

HRID 651636Notes

Reaction equation

HRID 651636 reaction equation
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]1[CH:11]=[CH:10][N:9]=[CH:8][CH:7]=1.[Li]CCCC.[S:17](Cl)([Cl:20])(=[O:19])=[O:18]>C1COCC1>[N:9]1[CH:10]=[CH:11][C:6]([C:2]2[S:1][C:5]([S:17]([Cl:20])(=[O:19])=[O:18])=[CH:4][CH:3]=2)=[CH:7][CH:8]=1

Participants

5

Reactant 3

HCID 24648Sulfuryl chlorideHCID 5952454-(2-Thienyl)pyridineHCID 178418339Butyllithium

Product 1

HCID 106350455-Pyridin-4-yl-thiophene-2-sulfonyl chlorideYield 63.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4-thiophen-2-yl-pyridine (3.33 g, 20.7 mmol) in THF (137 mL) at −78° C. is added n-BuLi (8.7 mL of a 2.5 M solution in hexanes, 21.7 mmol). After stirring for 15 minutes, SO2 gas is bubbled through the solution for 30 minutes. The solution is then allowed to warm to room temperature and stirred overnight. The solution is concentrated to dryness and the resulting solid is suspended in hexane (100 ml). To the ice-cooled solution is added sulfuryl chloride (1.7 mL. 21.7 mmol). The ice bath is removed and the suspension is stirred for 2 hours. The mixture is then concentrated to dryness and diluted with ethyl acetate and washed with saturated NaHCO3 (aq), water and brine. The organic layer is dried over MgSO4, filtered and concentrated to give a yellow solid as the title product (3.39 g, 13.1 mmol) which is used in the subsequent step without further purification.

Workup

  1. customSO2 gas is bubbled through the solution for 30 minutes
  2. stirringstirred overnight
  3. concentrationThe solution is concentrated to dryness
  4. temperatureTo the ice-cooled solution
  5. customThe ice bath is removed
  6. stirringthe suspension is stirred for 2 hours
  7. concentrationThe mixture is then concentrated to dryness
  8. additiondiluted with ethyl acetate
  9. washwashed with saturated NaHCO3 (aq), water and brine
  10. dry with materialThe organic layer is dried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-1f2634f725be4e9eb52bf28ed36bcb47
Source dataset
uspto-grants-2001_08
Patent number
US06281227B1

Reaction notes

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