Triethylborane → 4-[2-(3-Chloro-4-methyl-phenyl)-4-trifluoromethyl-imidazol-1-yl]-benzenesulfonamide

HRID 52336

Reaktionsgleichung

Reaktionsgleichung von HRID 52336
[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[N:10]([C:18]3[CH:23]=[CH:22][C:21]([S:24](C)(=[O:26])=[O:25])=[CH:20][CH:19]=3)[CH:11]=[C:12]([C:14]([F:17])([F:16])[F:15])[N:13]=2)[CH:5]=[CH:6][C:7]=1[CH3:8].C([Mg]Cl)CCC.C(B(CC)CC)C.C([O-])(=O)C.[Na+].[NH2:46]OS(O)(=O)=O>O1CCCC1.O>[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[N:10]([C:18]3[CH:23]=[CH:22][C:21]([S:24]([NH2:46])(=[O:26])=[O:25])=[CH:20][CH:19]=3)[CH:11]=[C:12]([C:14]([F:17])([F:16])[F:15])[N:13]=2)[CH:5]=[CH:6][C:7]=1[CH3:8]

Komponenten

8

Edukt 5

HCID 7357TriethylboraneHCID 76284hydroxylamine-O-sulfonic acidHCID 517045Sodium AcetateHCID 105019571h-Imidazole,2-(3-chloro-4-methylphenyl)-1-[4-(methylsulfonyl)phenyl]-4-(trifluoromethyl)-HCID 178418265HCID 178418265, Verbindung

Produkt 1

HCID 101588064-[2-(3-Chloro-4-methyl-phenyl)-4-trifluoromethyl-imidazol-1-yl]-benzenesulfonamideAusbeute 36,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a clear solution of 2-(3-chloro-4-methylphenyl) -1-[4-(methylsulfonyl)phenyl]-4-(trifluoromethyl)-1H-imidazole (Example 16) (500 mg, 1.2 mmol) in tetrahydrofuran (10 mL) at 0° C., n-BuMgCl (2M solution in THF, 2.4 mL, 4.8 mmol) was added over 10 minutes. After stirring for additional 10 minutes, ice bath was removed and solution stirred for 1 hour. The reaction mixture was re-cooled to 0° C. and triethylborane (1M solution in THF, 6 mL, 6 mmol) was added. After stirring for 2 hours, the reaction was heated to reflux for 72 hours. The reaction mixture was cooled to room temperature and treated with aqueous sodium acetate (1 g in 4 mL water). After stirring for 5 minutes, solid hydroxylamine-O-sulfonic acid (1 g) was added and the mixture stirred for 20 hours. The reaction mixture was diluted with water and extracted with ether (2×250). The ethereal layer was dried over sodium sulfate, filtered and concentrated in vacuo. The crude product (710 mg) was chromatographed (silica gel, ethyl acetate/toluene 3/7) to give pure 4-[2-(3-chloro-4-methylphenyl)-4-(trifluoromethyl)-1H-imidazol-1-yl]benzenesulfonamide (180 mg, 36%) as a white solid: mp(DSC) 222° C. Anal. Calc'd. for C17H13N3SO2F3Cl: C, 49.10, H, 3.15, N, 10.11. Found: C, 49.42, H, 3.19, N, 9.75.

Aufarbeitung

  1. customice bath was removed
  2. stirringsolution stirred for 1 hour
  3. stirringAfter stirring for 2 hours
  4. temperaturethe reaction was heated
  5. temperatureto reflux for 72 hours
  6. temperatureThe reaction mixture was cooled to room temperature
  7. stirringAfter stirring for 5 minutes
  8. stirringthe mixture stirred for 20 hours
  9. extractionextracted with ether (2×250)
  10. dry with materialThe ethereal layer was dried over sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. customThe crude product (710 mg) was chromatographed (silica gel, ethyl acetate/toluene 3/7)

Quellen und Nachweise

ORD-Eintrag
ord-30e70d6c6f764cf4a332ce6b2a3fa7e6
Quelldatensatz
uspto-grants-1997_04
Patentnummer
US05616601

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