3-fluorodibenzo[b,e]oxepin-11(6H)-one → 3-Fluoro-6,11-dihydro-11-methylenedibenz[b,e]oxepin

HRID 1716377Notes

Reaction equation

HRID 1716377 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11](=O)[C:10]3[CH:13]=[CH:14][CH:15]=[CH:16][C:9]=3[CH2:8][O:7][C:6]=2[CH:17]=1.[CH3:18][Mg+].[Br-]>C1COCC1>[F:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11](=[CH2:18])[C:10]3[CH:13]=[CH:14][CH:15]=[CH:16][C:9]=3[CH2:8][O:7][C:6]=2[CH:17]=1

Participants

4

Reactant 2

HCID 110751573-fluorodibenzo[b,e]oxepin-11(6H)-oneHCID 178418689HCID 178418689, compound

Product 1

HCID 588114773-Fluoro-6,11-dihydro-11-methylenedibenz[b,e]oxepinYield 81%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Cool a solution of 3-fluoro-6H-dibenzo[b,e]oxepin-11-one (prepared according to the procedure reported by M Kurokawa, F Sato, Y Masuda, T Yoshida and Y Ochi, Chem. Pharm. Bull., 1991, 39(10), 2564-5273; 11.5 g, 50.5 mmol) and THF (100 mL) to 0° C. under N2. Add dropwise MeMgBr (3.0M in Et2O, 33.7 mL, 101 mmol) this mixture. Warm to room temperature and stir overnight. Cool to 0° C. and quench very carefully (exotherm) with HCl (4.00 M in dioxane, 30 mL). Warm to room temperature and stir for 30 min. Dilute reaction mixture with water (70 mL) and extract into ethyl acetate (three 100 mL portions). Dry (MgSO4), filter, and concentrate organics to a brown solid. Purify crude product on a 100 g plug of silica gel, eluting with hexanes to afford 9.26 g (81%) of the title compound as a yellow solid. MS [EI] 226; HPLC shows 90% purity.

Workup

  1. customprepared
  2. customto 0° C.
  3. temperatureCool to 0° C.
  4. customquench very carefully (exotherm) with HCl (4.00 M in dioxane, 30 mL)
  5. temperatureWarm to room temperature
  6. stirringstir for 30 min
  7. additionDilute
  8. customreaction mixture with water (70 mL)
  9. extractionextract into ethyl acetate (three 100 mL portions)
  10. dry with materialDry (MgSO4)
  11. filtrationfilter
  12. concentrationconcentrate organics to a brown solid
  13. customPurify crude product on a 100 g plug of silica gel
  14. washeluting with hexanes

Sources & evidence

ORD record
ord-3efb12e2fec347cd905aa5b4032655e7
Source dataset
uspto-grants-2010_09
Patent number
US07803814B2

Reaction notes

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