Chlorosulfonic acid → 3-Methyl-4-(2,2,2-trifluoroacetamido)benzene-1-sulfonyl chloride

HRID 2273982Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2273982
[Cl:1][S:2]([OH:5])(=O)=[O:3].[F:6][C:7]([F:19])([F:18])[C:8]([NH:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[CH3:17])=[O:9]>>[CH3:17][C:12]1[CH:13]=[C:14]([S:2]([Cl:1])(=[O:5])=[O:3])[CH:15]=[CH:16][C:11]=1[NH:10][C:8](=[O:9])[C:7]([F:6])([F:18])[F:19]

Komponenten

3

Edukt 2

HCID 24638Chlorosulfonic acidHCID 137696Acetamide, 2,2,2-trifluoro-N-(2-methylphenyl)-

Produkt 1

HCID 536276703-Methyl-4-(2,2,2-trifluoroacetamido)benzene-1-sulfonyl chlorideAusbeute 69 %

Versuchsvorschrift

16.43 mL (5.00 equiv.) Chlorosulfonic acid was cooled in an aceton/ice-bath and 10.00 g 2,2,2-trifluoro-N-o-tolyl-acetamide was added in three portions, keeping the reaction mixture temperature below 5° C. The ice-bath was removed, the pale yellow mixture was allowed to warm to room temperature and then heated on an oil bath of 70° C. for 5.5 hours. The oil bath was removed and at about 30-35° C. the brown mixture was poured very carefully into a beaker with ice (exotermic, copious amounts of HCl evolve), giving a thick, gummy and very sticky precipitate. The mixture was extracted three times with DCM and the combined organic layers were washed with brine, dried over Na2SO4, filtered and evaporated onto silica. Purification with flash chromatography (EtOAc/PA 1:9→1:4) yielded 10.3 g (69%) of a white solid. 1H NMR (400 MHz, CDCl3) δ 2.46 (s, 3H), 7.90 (br.s., 1H), 7.94 (s, 1H), 7.98 (dd, J=8.6, 2.15 Hz, 1H), 8.35 (d, J=8.6 Hz, 1H).

Aufarbeitung

  1. customthe reaction mixture temperature below 5° C
  2. customThe ice-bath was removed
  3. temperatureheated on an oil bath of 70° C. for 5.5 hours
  4. customThe oil bath was removed and at about 30-35° C. the brown mixture
  5. additionwas poured very carefully into a beaker with ice (exotermic, copious amounts of HCl evolve)
  6. customgiving a thick, gummy and very sticky precipitate
  7. extractionThe mixture was extracted three times with DCM
  8. washthe combined organic layers were washed with brine
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. customevaporated onto silica
  12. customPurification with flash chromatography (EtOAc/PA 1:9→1:4)

Quellen und Nachweise

ORD-Eintrag
ord-c8b80c902521479db92c40a960f9e5b0
Quelldatensatz
uspto-grants-2015_09
Patentnummer
US09126942B2

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