3-fluoro-6,10b-dihydro-1aH-dibenzo-[3,4:6,7]cyclohept[1,2-b]oxirene → HCID 59465446, compound

HRID 2250838Notes

Reaction equation

HRID 2250838 reaction equation
Br[Mg][CH2:3][CH:4]=[CH2:5].[F:6][C:7]1[CH:8]=[CH:9][C:10]2[CH2:17][C:16]3[CH:18]=[CH:19][CH:20]=[CH:21][C:15]=3[CH:13]3[O:14][CH:12]3[C:11]=2[CH:22]=1>O1CCCC1>[F:6][C:7]1[CH:8]=[CH:9][C:10]2[CH2:17][C:16]3[CH:18]=[CH:19][CH:20]=[CH:21][C:15]=3[C@@H:13]([CH2:5][CH:4]=[CH2:3])[C@H:12]([OH:14])[C:11]=2[CH:22]=1.[F:6][C:7]1[CH:8]=[CH:9][C:10]2[CH2:17][C:16]3[CH:18]=[CH:19][CH:20]=[CH:21][C:15]=3[C@@H:13]([OH:14])[C@H:12]([CH2:5][CH:4]=[CH2:3])[C:11]=2[CH:22]=1

Participants

5

Reactant 2

HCID 865887003-fluoro-6,10b-dihydro-1aH-dibenzo-[3,4:6,7]cyclohept[1,2-b]oxireneHCID 178455850HCID 178455850, compound

Product 2

HCID 59465446HCID 59465446, compoundYield 36%HCID 69309571(trans)-2-fluoro-10,11-dihydro-11-(2-propenyl)-5H-dibenzo[a,d]cyclohepten-10-olYield 19%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Bromo-2-propenyl-magnesium (0.0542 mol) was added dropwise to a solution of intermediate 2 (0.04956 mol) in tetrahydrofuran (120 ml) under N2 atmosphere. The reaction mixture was stirred for 30 minutes at room temperature, then stirred and refluxed for 2 hours. The reaction mixture was cooled on an ice-bath, quenched with a 20% NH4Cl solution, and extracted with ethyl acetate. The organic layer was separated, dried, filtered and the solvent was evaporated. The residue was purified and separated into two regio-isomers by HPLC over silica gel (eluent: hexanes/ethyl acetate 9/1). Two pure fraction groups were collected and their solvent was evaporated, yielding 4.79 g (36%) of (±)-trans-8-fluoro-10,11-dihydro-11-(2-propenyl)-5H-dibenzo[a,d]cyclo-hepten-10-ol (intermediate 3) and 2.52 g (19%) of (trans)-2-fluoro-10,11-dihydro-11-(2-propenyl)-5H-dibenzo[a,d]cyclohepten-10-ol (intermediate 4).

Workup

  1. stirringstirred
  2. temperaturerefluxed for 2 hours
  3. temperatureThe reaction mixture was cooled on an ice-bath
  4. customquenched with a 20% NH4Cl solution
  5. extractionextracted with ethyl acetate
  6. customThe organic layer was separated
  7. customdried
  8. filtrationfiltered
  9. customthe solvent was evaporated
  10. customThe residue was purified
  11. customseparated into two regio-isomers by HPLC over silica gel (eluent: hexanes/ethyl acetate 9/1)
  12. customTwo pure fraction groups were collected
  13. customtheir solvent was evaporated

Sources & evidence

ORD record
ord-a079a7f9fc9d4deeb3943a38edc5d6f9
Source dataset
uspto-grants-2008_01
Patent number
US07317115B2

Reaction notes

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