Hexane → 4-[4-(4-Fluorophenyl)thien-3-yl]benzenesulfonamide

HRID 1743891ノート

反応式

HRID 1743891 の反応式
C[S:2]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[C:15]([C:16]3[CH:21]=[CH:20][C:19]([F:22])=[CH:18][CH:17]=3)=[CH:14][S:13][CH:12]=2)=[CH:7][CH:6]=1)(=[O:4])=[O:3].C([Li])CCC.CCCCCC.C(B(CCCC)CCCC)CCC.C([O-])(=O)C.[Na+].[NH2:52]OS(O)(=O)=O>C1COCC1.C(OCC)(=O)C.O>[F:22][C:19]1[CH:20]=[CH:21][C:16]([C:15]2[C:11]([C:8]3[CH:9]=[CH:10][C:5]([S:2]([NH2:52])(=[O:4])=[O:3])=[CH:6][CH:7]=3)=[CH:12][S:13][CH:14]=2)=[CH:17][CH:18]=1

参加物

10

反応物 6

HCID 8058HexaneHCID 31216TributylboraneHCID 76284hydroxylamine-O-sulfonic acidHCID 517045Sodium AcetateHCID 104268843-(4-Methylsulfonylphenyl)-4-(4-fluorophenyl)thiopheneHCID 178418339Butyllithium

生成物 1

HCID 120886704-[4-(4-Fluorophenyl)thien-3-yl]benzenesulfonamide収率 17.7%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
-70 °C

実験手順

To a solution of 3-(4-methylsulfonylphenyl)-4-(4-fluorophenyl)thiophene (0.332 g, 1.0 mmol) in THF (8 mL) at −70° C. under nitrogen was added 1.6 M n-butyl lithium in hexane (0.66 mL, 1.05 mmol) slowly, via syringe, and the mixture stirred at −70° C. for 20 minutes and then at room temperature (25° C.) for 1 hour. After cooling to −70° C., a 1.0 M solution of tri-n-butyl borane in THF (1.15 mL, 1.15 mmol) was added and the mixture allowed to warm slowly to 0° C. for 1 hour, warmed to room temperature for 2 hours, and finally stirred at reflux overnight (18 hours). After cooling to room temperature and stirring for 3 hours, water (0.8 mL) was added followed by sodium acetate (0.6 g) and hydroxylamine-O-sulfonic acid (0.41 g). After stirring at room temperature. overnight, the mixture was poured into 3 volumes of ethyl acetate, and the organic layer washed with water and brine and dried over MgSO4. After solvent removal, the white solids (a mixture of product and starting material) were separated via flash chromatography on silica gel using a 15% ethyl acetate/85% toluene eluant to yield the benzenesulfonamide as a white solid (59 mg, mp 194–195° C.). Anal. Calc'd for C16H12NO2S2F: C, 57.64; H, 3.63; N, 4.20. Found: C, 57.37; H, 3.69; N, 3.99.

後処理

  1. waitat room temperature (25° C.) for 1 hour
  2. temperatureAfter cooling to −70° C.
  3. temperatureto warm slowly to 0° C. for 1 hour
  4. temperaturewarmed to room temperature for 2 hours
  5. stirringfinally stirred
  6. temperatureat reflux overnight (18 hours)
  7. temperatureAfter cooling to room temperature
  8. stirringstirring for 3 hours
  9. stirringAfter stirring at room temperature
  10. washthe organic layer washed with water and brine
  11. dry with materialdried over MgSO4
  12. customAfter solvent removal
  13. additionthe white solids (a mixture of product and starting material)
  14. customwere separated via flash chromatography on silica gel using a 15% ethyl acetate/85% toluene eluant

出典と根拠

ORDレコード
ord-5173cc0db09c45398c2151f9fc0ebf8a
出典データセット
uspto-grants-2006_03
特許番号
US07012094B1

反応ノート

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