Pyridine → 4-Phenylbicyclo[2.2.2]oct-1-ylmethyl toluene-4-sulfonate

HRID 2353084ノート

反応式

HRID 2353084 の反応式
N1C=CC=CC=1.[C:7]1([CH3:17])[CH:12]=[CH:11][C:10]([S:13](Cl)(=[O:15])=[O:14])=[CH:9][CH:8]=1.[C:18]1([C:24]23[CH2:31][CH2:30][C:27]([CH2:32][OH:33])([CH2:28][CH2:29]2)[CH2:26][CH2:25]3)[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>C(Cl)Cl.CN(C)C1C=CN=CC=1>[C:7]1([CH3:17])[CH:12]=[CH:11][C:10]([S:13]([O:33][CH2:32][C:27]23[CH2:26][CH2:25][C:24]([C:18]4[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=4)([CH2:29][CH2:28]2)[CH2:31][CH2:30]3)(=[O:15])=[O:14])=[CH:9][CH:8]=1

参加物

6

反応物 3

HCID 1049Pyridine2 回HCID 73974-Toluenesulfonyl chloride2 回HCID 21675352(4-Phenylbicyclo[2.2.2]oct-1-yl)methanol

生成物 1

HCID 866252464-Phenylbicyclo[2.2.2]oct-1-ylmethyl toluene-4-sulfonate収率 89.2%

試薬・触媒・溶媒 2

HCID 142844-(Dimethylamino)pyridine触媒HCID 6344Dichloromethane溶媒4 回

反応条件

温度
2.5 °C

実験手順

Pyridine (4 mL), then a solution of toluene-4-sulfonyl chloride (7.4 g, 38.81 mmol) in dry DCM (30 mL), were added to a stirred solution of (4-phenylbicyclo[2.2.2]oct-1-yl)methanol (7.0 g, 32.36 mmol) in DCM (70 mL), maintaining 0-5° C. throughout. The reaction mixture was stirred at 0° C. overnight, refluxed for 2 h then cooled to 35° C. Further pyridine (2 mL) and a solution of toluene-4-sulfonyl chloride (3.9 g) in DCM (10 mL) were added and the mixture stirred at reflux for 2 h. As some starting material remained, a catalytic amount of 4-dimethylaminopyridine was added and the mixture stirred under reflux overnight. The mixture was cooled, diluted with DCM (200 mL) then washed with water (100 mL), hydrochloric acid (2M; 150 mL), water (50 mL), sat. aq. NaHCO3 (100 mL), water (50 mL) and brine (50 mL). After drying (MgSO4) the solution was concentrated to give crude product which was purified by silica column chromatography (silica 40-63 micron) eluting with hexane:ethyl acetate (19:1 to 4:1) to afford the title compound as a pale yellow solid (10.7 g, 89%).

後処理

  1. temperaturerefluxed for 2 h
  2. temperaturethen cooled to 35° C
  3. stirringthe mixture stirred
  4. temperatureat reflux for 2 h
  5. stirringthe mixture stirred
  6. temperatureunder reflux overnight
  7. temperatureThe mixture was cooled
  8. washthen washed with water (100 mL), hydrochloric acid (2M; 150 mL), water (50 mL), sat. aq. NaHCO3 (100 mL), water (50 mL) and brine (50 mL)
  9. dry with materialAfter drying (MgSO4) the solution
  10. concentrationwas concentrated
  11. customto give crude product which
  12. customwas purified by silica column chromatography (silica 40-63 micron)
  13. washeluting with hexane:ethyl acetate (19:1 to 4:1)

出典と根拠

ORDレコード
ord-dc873e5d2d104c9ba718de4863790f26
出典データセット
uspto-grants-2010_07
特許番号
US07749997B2

反応ノート

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