Hydrofluoric Acid → 5-benzyl-10-fluoro-5H-dibenz[b,f]azepine

HRID 616884

Reaktionsgleichung

Reaktionsgleichung von HRID 616884
[CH2:1]([N:8]1[C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=2[C:12](=O)[CH2:11][C:10]2[CH:20]=[CH:21][CH:22]=[CH:23][C:9]1=2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.F.S(F)(F)(F)[F:26]>C(Cl)Cl>[CH2:1]([N:8]1[C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=2[C:12]([F:26])=[CH:11][C:10]2[CH:20]=[CH:21][CH:22]=[CH:23][C:9]1=2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Komponenten

5

Edukt 3

HCID 14917Hydrofluoric AcidHCID 24555Sulfur tetrafluorideHCID 133529325-Benzyl-10-oxo-10,11-dihydro-5H-dibenz[b,f]azepine

Produkt 1

HCID 203664075-benzyl-10-fluoro-5H-dibenz[b,f]azepine

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

A mixture of 149.7 g (0.5 mole) of 5-benzyl-5,11-dihydro-10H-dibenz[b,f]azepin-10-one (vide British Pat. No. 961 444),27 ml of hydrogen fluoride, 125 g of sulphur tetrafluoride and 400 ml of methylene chloride is heated in a steel autocalve for 16 hours to 70° C. After the mixture has cooled, the bulk of the liquid constituents are filtered off with suction. Then water and aqueous ammonia solution are added until the pH of the aqueous phase is 9-10. The organic phase is separated, washed three times with water, diluted with 200 ml of benzene and concentrated in a rotary evaporator. The black residue is dissolved in methylene chloride and the solution is filtered through 700 g of silica gel (particle size 0.063-0.2 mm) with methylene chloride as eluant. The filtrate is concentrated, the residue dissolved in 1.5 liters of benzene and stirred for 30 minutes with 500 g of magnesium silicate gel. The mixture is filtered and 500 g of magnesium silicate gel are again added to the filtrate. After repeated filtration, the solution is concentrated in vacuo and the black residue is chromatographed over 800 g of silica gel (particle size 0.063-0.2 mm) with hexane/benzene (2:1) as eluant. The homogeneous fractions are combined and concentrated to yield the 5-benzyl-10-fluoro-5H-dibenz[b,f]azepine as a light yellow oil.

Aufarbeitung

  1. temperatureAfter the mixture has cooled
  2. filtrationthe bulk of the liquid constituents are filtered off with suction
  3. additionThen water and aqueous ammonia solution are added until the pH of the aqueous phase
  4. customThe organic phase is separated
  5. washwashed three times with water
  6. additiondiluted with 200 ml of benzene
  7. concentrationconcentrated in a rotary evaporator
  8. dissolutionThe black residue is dissolved in methylene chloride
  9. filtrationthe solution is filtered through 700 g of silica gel (particle size 0.063-0.2 mm) with methylene chloride as eluant
  10. concentrationThe filtrate is concentrated
  11. dissolutionthe residue dissolved in 1.5 liters of benzene
  12. filtrationThe mixture is filtered
  13. addition500 g of magnesium silicate gel are again added to the filtrate
  14. filtrationfiltration
  15. concentrationthe solution is concentrated in vacuo
  16. customthe black residue is chromatographed over 800 g of silica gel (particle size 0.063-0.2 mm) with hexane/benzene (2:1) as eluant
  17. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-6e16e1d325b246158c6043cb965b24b3
Quelldatensatz
uspto-grants-1978_02
Patentnummer
US04076812

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