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

HRID 726697

反応式

HRID 726697 の反応式
[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

参加物

7

反応物 3

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

生成物 1

HCID 108065444-Fluoro-1-tosyl-3,4-dihydro-1H-benzo[B]azepin-5(2H)-one収率 78.6%

試薬・触媒・溶媒 3

HCID 7912Diisopropylamine溶媒HCID 8028Tetrahydrofuran溶媒3 回HCID 178418339Butyllithium溶媒

反応条件

温度
-78 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-36a13314ff624c58a2aac0bd6920f476
出典データセット
uspto-grants-1998_01
特許番号
US05710150

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