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

HRID 1396067ノート

反応式

HRID 1396067 の反応式
[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]

参加物

3

反応物 2

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

生成物 1

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

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-e75c441e10f54bd8adb2b60aaf49f2ad
出典データセット
uspto-grants-2014_12
特許番号
US08901108B2

反応ノート

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