Pyridine → Tris-(4-butoxyphenyl) sulfonium nonafluorobutane sulfonate

HRID 277691노트

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HRID 277691 반응식
[C:1]([O:5][C:6]1[CH:11]=[CH:10][C:9]([S:12]([C:14]2[CH:19]=[CH:18][C:17]([O:20]C(C)(C)C)=[CH:16][CH:15]=2)=O)=[CH:8][CH:7]=1)(C)(C)[CH3:2].N1[CH:30]=[CH:29][CH:28]=[CH:27]C=1.[F:31][C:32]([F:51])([F:50])[C:33]([F:49])([F:48])[C:34]([F:47])([F:46])[C:35]([F:45])([F:44])[S:36]([O:39][Si](C)(C)C)(=[O:38])=[O:37].[Mg].[C:53]([O:57][C:58]1[CH:63]=[CH:62][C:61](Cl)=[CH:60][CH:59]=1)([CH3:56])(C)C.O1CC[CH2:67][CH2:66]1>O>[F:51][C:32]([F:31])([F:50])[C:33]([F:48])([F:49])[C:34]([F:46])([F:47])[C:35]([F:44])([F:45])[S:36]([O-:39])(=[O:38])=[O:37].[CH2:53]([O:57][C:58]1[CH:59]=[CH:60][C:61]([S+:12]([C:9]2[CH:10]=[CH:11][C:6]([O:5][CH2:1][CH2:2][CH2:66][CH3:67])=[CH:7][CH:8]=2)[C:14]2[CH:15]=[CH:16][C:17]([O:20][CH2:30][CH2:29][CH2:28][CH3:27])=[CH:18][CH:19]=2)=[CH:62][CH:63]=1)[CH2:56][CH2:32][CH3:33]

참가 물질

8

반응물 6

HCID 1049PyridineHCID 8028Tetrahydrofuran2회HCID 1404581-Chloro-4-tert-butoxybenzeneHCID 2778025Trimethylsilyl nonafluorobutanesulfonateHCID 5462224MagnesiumHCID 15389810Bis(4-tert-butoxyphenyl) sulfoxide

생성물 1

HCID 22599127Tris-(4-butoxyphenyl) sulfonium nonafluorobutane sulfonate

시약·촉매·용매 1

HCID 962Water용매

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온도
5 °C

실험 절차

To a stirred solution of 60.0 g (0.164 mol) of bis-(4-t-butoxyphenyl) sulfoxide in 26.8 g (0.34 mol) of pyridine and 400 ml of tetrahydrofuran was dropped 126.57 g (0.34 mol) of trimethylsilyl nonafluorobutane sulfonate while keeping the temperature below −5° C. with a salted ice bath. After completion of the addition, the reaction temperature was raised to 5° C., followed by stirring for additional 20 minutes. A Grignard solution was prepared from 8.4 g (0.34 mol) of magnesium, 100 g of tetrahydrofuran and 68.6 g (0.38 mol) of 4-t-butoxy chlorobenzene, and added dropwise to the above solution at 0° C. The mixture was stirred for 2 hours at this temperature. Then water was added to decompose the excess Grignard reagent, and the inorganic salts were removed by filtration. The solution was concentrated to about 160 ml and extracted with a mixture of 1200 ml of dichloromethane, 600 g of a saturated aqueous solution of ammonium chloride and 600 ml water. The organic phase was washed twice with water and dried. The solvent was removed to yield an oily product which was then purified by column chromatography on silica gel using dichloromethane as the eluant. Thus, tris-(4-butoxyphenyl) sulfonium nonafluorobutane sulfonate was obtained as a slightly yellowish powder. The structure was confirmed by 1H-NMR (CDCl3) with δ=1.42 (s, 27H), 7.35-7.42 (d, 6H) and 7.78-7.93 ppm (d, 6H).

후처리

  1. customthe temperature below −5° C.
  2. additionAfter completion of the addition
  3. additionadded dropwise to the above solution at 0° C
  4. stirringThe mixture was stirred for 2 hours at this temperature
  5. customthe inorganic salts were removed by filtration
  6. concentrationThe solution was concentrated to about 160 ml
  7. extractionextracted with a mixture of 1200 ml of dichloromethane, 600 g of a saturated aqueous solution of ammonium chloride and 600 ml water
  8. washThe organic phase was washed twice with water
  9. customdried
  10. customThe solvent was removed
  11. customto yield an oily product which
  12. customwas then purified by column chromatography on silica gel

출처 및 근거

ORD 기록
ord-dbdb04ba93d54eb48bac2a35956627ae
출처 데이터셋
uspto-grants-2002_03
특허 번호
US06358665B1

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