Tributylborane → 4-[2(4-Fluorophenyl)-4,4-dimethylcyclopenten-1-yl)benzenesulfonamide

HRID 1901105노트

반응식

HRID 1901105 반응식
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:12][C:11]([CH3:14])([CH3:13])[CH2:10][C:9]=2[C:15]2[CH:20]=[CH:19][C:18]([S:21](C)(=[O:23])=[O:22])=[CH:17][CH:16]=2)=[CH:4][CH:3]=1.C(B(CCCC)CCCC)CCC.C([O-])(=O)C.[Na+].O[NH:44]S(O)(=O)=O>C1COCC1.C([Li])CCC.O>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:12][C:11]([CH3:14])([CH3:13])[CH2:10][C:9]=2[C:15]2[CH:20]=[CH:19][C:18]([S:21]([NH2:44])(=[O:23])=[O:22])=[CH:17][CH:16]=2)=[CH:4][CH:3]=1

참가 물질

8

반응물 4

HCID 31216TributylboraneHCID 170246Hydroxysulfamic acidHCID 517045Sodium AcetateHCID 98410791-[2-(4-Fluorophenyl)-4,4-dimethyl-1-cyclopentenyl]-4-methylsulfonylbenzene

생성물 1

HCID 102690884-[2(4-Fluorophenyl)-4,4-dimethylcyclopenten-1-yl)benzenesulfonamide수율 43.9%

시약·촉매·용매 3

HCID 178418339Butyllithium촉매HCID 962Water용매HCID 8028Tetrahydrofuran용매

실험 절차

Under nitrogen, a solution of 4.55 g (13.2 mmol) of 1-[2-(4-fluoro phenyl)-4,4-dimethylcyclopenten-1-yl]-4-(methylsulfonyl)benzene (from Step 10 of Example 1) in 50 mL of THF at -78° C. was treated with 6.3 mL (0.27 mmol) of n-butyllithium (2.5M in hexane) over a period of 5 minutes. The reaction was stirred at ambient temperature for 25 minutes, cooled to -78° C., and treated with 19.8 mL (19.8 mmol ) of tributylborane (1.0M in THF). The resulting dark brown solution was stirred at ambient temperature for 30 minutes and then at reflux for 14 hours prior to the addition of 8.7 g (106 mmol) of sodium acetate, 37 mL of water, and 5.2 g (46 mmol) of hydroxyamine-O-sulfonic acid. The resulting light orange mixture was stirred at ambient temperature for 6 hours and the aqueous phase extracted with ethyl acetate. The combined extracts were washed with water, brine, dried (MgSO4), and concentrated in vacuo. The residue was chromatographed on silica gel to give 2.0 g (40%) of 4-[2(4-fluorophenyl)-4,4-dimethylcyclopenten-1-yl)benzenesulfonamide as a colorless solid: mp 117°-118° C.; NMR (CDCl3) δ1.24 (s, 6H), 2.70 (s, 4H), 4.72 (s, 2H), 6.92 (t, J=9 Hz, 2H), 7.09 (dd, J=9 and 7 Hz, 2H), 7.26 (d, J=8 Hz, 2H), 7.74 (d, J=9 Hz, 2H). HRMS. Calc'd for C19H20FNO2S: 345.1199. Found: 345.1194. Anal. Calc'd for [C19H20FNO2S+0.27 H2O]: C, 65.14; H, 5.91; N, 4.00; S, 9.11. Found: C, 65.07; H, 5.94; N, 3.86; S, 9.29.

후처리

  1. temperaturecooled to -78° C.
  2. stirringThe resulting dark brown solution was stirred at ambient temperature for 30 minutes
  3. temperatureat reflux for 14 hours
  4. stirringThe resulting light orange mixture was stirred at ambient temperature for 6 hours
  5. extractionthe aqueous phase extracted with ethyl acetate
  6. washThe combined extracts were washed with water, brine
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. customThe residue was chromatographed on silica gel

출처 및 근거

ORD 기록
ord-dcde1b72b33b469e8079b2fa89e2a8d1
출처 데이터셋
uspto-grants-1996_11
특허 번호
US05576339

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