Chlorosulfonic acid → 5-Chloro-4-(2,5-difluorophenyl)thiophene-2-sulfonyl chloride

HRID 589678Notes

Reaction equation

HRID 589678 reaction equation
[Cl:1][C:2]1[S:3][CH:4]=[CH:5][C:6]=1[C:7]1[CH:12]=[C:11]([F:13])[CH:10]=[CH:9][C:8]=1[F:14].[Cl:15][S:16](O)(=[O:18])=[O:17]>C(Cl)Cl>[Cl:1][C:2]1[S:3][C:4]([S:16]([Cl:15])(=[O:18])=[O:17])=[CH:5][C:6]=1[C:7]1[CH:12]=[C:11]([F:13])[CH:10]=[CH:9][C:8]=1[F:14]

Participants

4

Reactant 2

HCID 24638Chlorosulfonic acidHCID 667999832-Chloro-3-(2,5-difluorophenyl)thiophene

Product 1

HCID 866891905-Chloro-4-(2,5-difluorophenyl)thiophene-2-sulfonyl chlorideYield 82.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 2-chloro-3-(2,5-difluorophenyl)thiophene (0.73 g, 3.2 mmol) in CH2Cl2 (100 mL), cooled on ice, chlorosulfonic acid (0.37 g, 3.2 mmol) in CH2Cl2 (50 mL) was added dropwise over 1 h. The reaction was refluxed over night. The reaction mixture was cooled and washed with water (2×100 mL) and brine, dried over MgSO4, filtered and concentrated to a dark brown oil. The oil was dissolved in heptane (50 mL) and stored in the fridge over the weekend. A black tar precipitated. The solution was decanted and concentrated to give the title compound as a light brown oil (0.87 g, 21% over two steps). MS (ESI+) m/z 293 [M−Cl]+.

Workup

  1. additionwas added dropwise over 1 h
  2. temperatureThe reaction was refluxed over night
  3. temperatureThe reaction mixture was cooled
  4. washwashed with water (2×100 mL) and brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated to a dark brown oil
  8. dissolutionThe oil was dissolved in heptane (50 mL)
  9. customA black tar precipitated
  10. customThe solution was decanted
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-782c4304aba54b2eb86a9801c492e56a
Source dataset
uspto-grants-2016_01
Patent number
US09233946B2

Reaction notes

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