Carbon Dioxide → Methyl 11-methoxy-6,11-dihydrodibenz[b,e]oxepin-3-carboxylate

HRID 1463904

Reaction equation

HRID 1463904 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[CH:11]([O:12][CH3:13])[C:10]3[CH:14]=[CH:15][CH:16]=[CH:17][C:9]=3[CH2:8][O:7][C:6]=2[CH:18]=1.C([Li])CCC.[CH3:24]CCCCC.[C:30](=[O:32])=[O:31].S(=O)(=O)(O)O>O1CCCC1.CO>[CH3:13][O:12][CH:11]1[C:10]2[CH:14]=[CH:15][CH:16]=[CH:17][C:9]=2[CH2:8][O:7][C:6]2[CH:18]=[C:2]([C:30]([O:32][CH3:24])=[O:31])[CH:3]=[CH:4][C:5]1=2

Participants

7

Reactant 4

HCID 280Carbon DioxideHCID 1118Sulfuric AcidHCID 150931363-Bromo-11-methoxy-6,11-dihydrodibenz[b,e]oxepineHCID 178418244HCID 178418244, compound

Product 1

HCID 9994021Methyl 11-methoxy-6,11-dihydrodibenz[b,e]oxepin-3-carboxylate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

3-Bromo-11-methoxy-6,11-dihydrodibenz[b,e]oxepine, 30 g, was dissolved in 500 ml of tetrahydrofuran. After cooling to -78° C., 65 ml of 1.6N n-butyl lithium/hexane solution was dropwise added to the solution in a nitrogen atmospher followed by stirring at -78° C. for further 40 minutes. The reaction solution was dropwise added onto 100 g of dry ice, which was allowed to stand to elevate to room temperature. The solvent was distilled off under reduced pressure. To the residue obtained, were added 500 ml of methanol and 10 ml of conc. sulfuric acid. The mixture was heated to reflux for 2 hours. After allowing to cool, the solvent was distilled off under reduced pressure. The residue was extracted with 500 ml of ethyl acetate. After washing successively with saturated sodium chloride aqueous solution, saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution, the extract was dried over anhydrous magnesium sulfate. The solvent was then distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (eluting solvent; hexane:ethyl acetate=1:1) to give 19.3 g of the product as pale yellow oil.

Workup

  1. customto elevate to room temperature
  2. distillationThe solvent was distilled off under reduced pressure
  3. customTo the residue obtained
  4. temperatureThe mixture was heated
  5. temperatureto reflux for 2 hours
  6. temperatureto cool
  7. distillationthe solvent was distilled off under reduced pressure
  8. extractionThe residue was extracted with 500 ml of ethyl acetate
  9. washAfter washing successively with saturated sodium chloride aqueous solution, saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution
  10. dry with materialthe extract was dried over anhydrous magnesium sulfate
  11. distillationThe solvent was then distilled off under reduced pressure
  12. washThe residue was subjected to silica gel column chromatography (eluting solvent; hexane:ethyl acetate=1:1)

Sources & evidence

ORD record
ord-8cdea2c11e484027aa97e4207aec3f04
Source dataset
uspto-grants-1994_04
Patent number
US05302596

Linked notes

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