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

HRID 359004

反応式

HRID 359004 の反応式
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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

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 atmosphere 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.

後処理

  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)

出典と根拠

ORDレコード
ord-4ab0094ac0c940db94692a59d6fd2258
出典データセット
uspto-grants-1991_03
特許番号
US04999363

関連ノート

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