Thionyl Chloride → 8-Bromo-7-fluoro-2,3,4,5-tetrahydro-3,5-methano-1H-2-benzazepin-1-one

HRID 575035Notes

Reaction equation

HRID 575035 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[F:12])[CH:8]1[CH2:13][CH:6]([CH2:7]1)[C:5]2=[N:14]O.S(Cl)(Cl)=[O:17]>O1CCOCC1>[Br:1][C:2]1[CH:3]=[C:4]2[C:9]([CH:8]3[CH2:13][CH:6]([NH:14][C:5]2=[O:17])[CH2:7]3)=[CH:10][C:11]=1[F:12]

Participants

4

Reactant 2

HCID 24386Thionyl ChlorideHCID 866930651,3-Methanonaphthalen-4(1H)-one, 6-bromo-7-fluoro-2,3-dihydro-, oxime

Product 1

HCID 866930678-Bromo-7-fluoro-2,3,4,5-tetrahydro-3,5-methano-1H-2-benzazepin-1-oneYield 89%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

Into a 100-mL round-bottom flask was placed a solution of 6-Bromo-7-fluoro-2,3-dihydro-1H-1,3-methano-naphthalen-4-one oxime (3.5 g, 12.96 mmol, 1.00 equiv) in 1,4-dioxane (30 mL) and thionyl chloride (24.7 g, 207.56 mmol, 16.00 equiv). The resulting solution was heated to reflux for 6 h, cooled, concentrated under vacuum, and quenched by the addition of 50 mL of water/ice. The solids were collected by filtration, washed with 2×50 mL of saturated aqueous NaHCO3 and 2×50 mL of water to afford 3.1 g (89%) of 5-bromo-4-fluoro-9-azatricyclo[8.1.1.0[2,7]]dodeca-2,4,6-trien-8-one as a white solid.

Workup

  1. customInto a 100-mL round-bottom flask was placed
  2. temperatureThe resulting solution was heated
  3. temperatureto reflux for 6 h
  4. temperaturecooled
  5. concentrationconcentrated under vacuum
  6. customquenched by the addition of 50 mL of water/ice
  7. filtrationThe solids were collected by filtration
  8. washwashed with 2×50 mL of saturated aqueous NaHCO3 and 2×50 mL of water

Sources & evidence

ORD record
ord-980789463a7748068d23b86154d9ece3
Source dataset
uspto-grants-2015_05
Patent number
US09034866B2

Reaction notes

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