Ammonium Chloride → 4-Fluoro-1-tosyl-3,4-dihydro-1H-benzo[B]azepin-5(2H)-one

HRID 726697

Reaktionsgleichung

Reaktionsgleichung von HRID 726697
[S:1]([N:11]1[C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][C:16]=2[C:15](=[O:22])[CH2:14][CH2:13][CH2:12]1)([C:4]1[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=1)(=[O:3])=[O:2].C1C=CC(S(N(S(C2C=CC=CC=2)(=O)=O)[F:33])(=O)=O)=CC=1.[Cl-].[NH4+]>O1CCCC1.C(NC(C)C)(C)C.C([Li])CCC>[F:33][CH:14]1[C:15](=[O:22])[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2[N:11]([S:1]([C:4]2[CH:5]=[CH:6][C:7]([CH3:8])=[CH:9][CH:10]=2)(=[O:2])=[O:3])[CH2:12][CH2:13]1

Komponenten

7

Edukt 3

HCID 25517Ammonium ChlorideHCID 2668521-Tosyl-3,4-dihydro-1H-benzo[b]azepin-5(2H)-oneHCID 588007N-Fluorobenzenesulfonimide

Produkt 1

HCID 108065444-Fluoro-1-tosyl-3,4-dihydro-1H-benzo[B]azepin-5(2H)-oneAusbeute 78,6 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 7912DiisopropylamineLösungsmittelHCID 8028TetrahydrofuranLösungsmittel3×HCID 178418339ButyllithiumLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

In 150 ml of tetrahydrofuran was dissolved 3.55 ml of diisopropylamine, and 14.9 ml of n-butyllithium was added dropwise while stirring at -78° C. in an atmosphere of argon. After 30 minutes of stirring under ice-cooling, the reaction mixture was cooled to -78° C., 60 ml of tetrahydrofuran solution containing 6.39 g of 1-tosyl-2,3,4,5-tetrahydro-1H-1-benzazepin-5-one was added dropwise thereto and the resulting mixture was stirred for 30 minutes. Then, 90 ml of tetrahydrofuran solution containing 8.94 g of N-fluorobenzenesulfonimide was added dropwise, and the mixture was stirred for 1 hour while gradually increasing the temperature to 0° C. After adding saturated ammonium chloride aqueous solution to the reaction solution, the mixture was concentrated under a reduced pressure. Ethyl acetate was added thereto to separate the water layer, and the organic layer was washed with saturated sodium thiosulfate aqueous solution, saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution in that order. The organic layer was then dried over anhydrous magnesium sulfate and concentrated under a reduced pressure. The resulting residue was applied to silica gel column chromatography, which was eluted with chloroform to obtain 5.31 g of 4-fluoro-1-tosyl-2,3,4,5-tetrahydro-1H-1-benzazepin-5-one.

Aufarbeitung

  1. additionwas added dropwise
  2. stirringAfter 30 minutes of stirring under ice-
  3. temperaturecooling
  4. temperaturethe reaction mixture was cooled to -78° C.
  5. additionwas added dropwise
  6. stirringthe resulting mixture was stirred for 30 minutes
  7. additionwas added dropwise
  8. stirringthe mixture was stirred for 1 hour
  9. temperaturewhile gradually increasing the temperature to 0° C
  10. concentrationthe mixture was concentrated under a reduced pressure
  11. additionEthyl acetate was added
  12. customto separate the water layer
  13. washthe organic layer was washed with saturated sodium thiosulfate aqueous solution, saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution in that order
  14. dry with materialThe organic layer was then dried over anhydrous magnesium sulfate
  15. concentrationconcentrated under a reduced pressure
  16. washwas eluted with chloroform

Quellen und Nachweise

ORD-Eintrag
ord-36a13314ff624c58a2aac0bd6920f476
Quelldatensatz
uspto-grants-1998_01
Patentnummer
US05710150

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