Sodium Sulfate → HCID 59632973, compound

HRID 2369076Notes

Reaction equation

HRID 2369076 reaction equation
Cl[S:2]([OH:5])(=[O:4])=[O:3].[Cl:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[N:13]1[C:17]([C:18]2[S:19][CH:20]=[CH:21][CH:22]=2)=[CH:16][C:15]([C:23]([F:26])([F:25])[F:24])=[N:14]1.[O-]S([O-])(=O)=O.[Na+].[Na+]>C(Cl)Cl>[Cl:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[N:13]1[C:17]([C:18]2[S:19][C:20]([S:2]([OH:5])(=[O:4])=[O:3])=[CH:21][CH:22]=2)=[CH:16][C:15]([C:23]([F:26])([F:24])[F:25])=[N:14]1

Participants

5

Reactant 3

HCID 24436Sodium SulfateHCID 24638Chlorosulfonic acidHCID 59633077HCID 59633077, compound

Product 1

HCID 59632973HCID 59632973, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

Chlorosulfonic acid (1.0 mL, 15 mmol) was added dropwise to a cold (−78° C.) solution of 1-(2-chlorophenyl)-5-(thiophen-2-yl)-3-(trifluoromethyl)-1H-pyrazole (1.0 g, 3.2 mmol) in CH2Cl2 (22 mL) After 75 minutes stirring at −78° C. the cooling bath was removed and the brown solution was allowed to warm to ambient temperature. After 3½ hours stirring at ambient temperature, the reaction mixture was poured onto ice and diluted with CH2Cl2. The milky lower organic phase was separated and dried over Na2SO4. Filtration and concentration under reduced pressure of the organics gave a biphasic mixture that was further pumped down under high vacuum. NMR and GC/MS analysis of this material showed it not to be the product. The aqueous phase from the workup was saturated with Na2SO4 and extracted with EtOAc (3×). These organic extract were dried over Na2SO4, filtered and concentrated under reduced pressure to afford 5-(1-(2-chlorophenyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl)thiophene-2-sulfonic acid as a yellow syrup. This crude material was carried on to the sulfonyl chloride formation without purification. MS(ES): 409[M+H]+.

Workup

  1. customwas removed
  2. temperatureto warm to ambient temperature
  3. stirringAfter 3½ hours stirring at ambient temperature
  4. additionthe reaction mixture was poured onto ice
  5. additiondiluted with CH2Cl2
  6. customThe milky lower organic phase was separated
  7. dry with materialdried over Na2SO4
  8. filtrationFiltration and concentration under reduced pressure of the
  9. customorganics gave a biphasic mixture that
  10. extractionextracted with EtOAc (3×)
  11. extractionThese organic extract
  12. dry with materialwere dried over Na2SO4
  13. filtrationfiltered
  14. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-03e6aa07a016416bb21f56c420ffac81
Source dataset
uspto-grants-2014_04
Patent number
US08703805B2

Reaction notes

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