Boron tribromide → 4-bromo-9a-butyl-8-chloro-6-fluoro-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one

HRID 7899Notes

Reaction equation

HRID 7899 reaction equation
[Br:1][C:2]1[C:3](=[O:23])[CH2:4][CH2:5][C:6]2([CH2:19][CH2:20][CH2:21][CH3:22])[C:14]=1[C:13]1[C:8](=[C:9]([Cl:18])[C:10]([O:16]C)=[C:11]([F:15])[CH:12]=1)[CH2:7]2.B(Br)(Br)Br>ClCCl>[Br:1][C:2]1[C:3](=[O:23])[CH2:4][CH2:5][C:6]2([CH2:19][CH2:20][CH2:21][CH3:22])[C:14]=1[C:13]1[C:8](=[C:9]([Cl:18])[C:10]([OH:16])=[C:11]([F:15])[CH:12]=1)[CH2:7]2

Participants

4

Reactant 2

HCID 25134Boron tribromideHCID 219908584-bromo-9a-butyl-8-chloro-6-fluoro-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one

Product 1

HCID 102936004-bromo-9a-butyl-8-chloro-6-fluoro-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 4-bromo-9a-butyl-8-chloro-6-fluoro-7-methoxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one (31 mg, 0.077 mmol) in anhydrous dichloromethane (0.5 mL) was cooled in a dry ice-acetone bath (−78° C.) and the solution treated with 1M boron tribromide in dichloromethane (0.231 mL, 0.231 mmol). The cooling bath was removed and the mixture was stirred at room temperature for one hour. The mixture was partitioned between EtOAc (20 mL) and water (20 mL) containing 2N HCl (2 mL). The organic phase was washed with brine (10 mL), dried over MgSO4, filtered, and evaporated under vacuum. The residue was purified by preparative layer chromatography on a 0.05×20×20 cm silica gel GF plate, developing with 10% EtOAc in CHCl2. The product band was eluted with EtOAc, the eluent evaporated under vacuum, and the residue lyophilized from benzene plus a few drops of EtOH to afford 4-bromo-9a-butyl-8-chloro-6-fluoro-7-hydroxy-1,2,9,9a-tetrahydro-3H-fluoren-3-one as an amorphous solid.

Workup

  1. customThe cooling bath was removed
  2. customThe mixture was partitioned between EtOAc (20 mL) and water (20 mL)
  3. additioncontaining 2N HCl (2 mL)
  4. washThe organic phase was washed with brine (10 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated under vacuum
  8. customThe residue was purified by preparative layer chromatography on a 0.05×20×20 cm silica gel GF plate
  9. washThe product band was eluted with EtOAc
  10. customthe eluent evaporated under vacuum

Sources & evidence

ORD record
ord-72b7c7dabe5b4cf6835bd1c3a2ab8214
Source dataset
uspto-grants-2006_08
Patent number
US07087599B2

Reaction notes

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