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

HRID 908127노트

반응식

HRID 908127 반응식
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

참가 물질

6

반응물 3

HCID 1049Pyridine2회HCID 73974-Toluenesulfonyl chloride2회HCID 21675352(4-Phenylbicyclo[2.2.2]oct-1-yl)methanol

생성물 1

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

시약·촉매·용매 2

HCID 142844-(Dimethylamino)pyridine촉매HCID 6344Dichloromethane용매4회

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온도
2.5 °C

실험 절차

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%).

후처리

  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)

출처 및 근거

ORD 기록
ord-ab5c9865091c4662befc51349245f348
출처 데이터셋
uspto-grants-2011_09
특허 번호
US08017603B2

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