Naphthacene → 5,12-Dihydro-5,12-ethanobenz[b]anthracene-13,14-diol

HRID 1448850

반응식

HRID 1448850 반응식
[CH:1]1[C:6]2=[CH:7][C:8]3[C:17]([CH:18]=[C:5]2[CH:4]=[CH:3][CH:2]=1)=[CH:16][C:15]1[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=1)[CH:9]=3.C1(=O)[O:23][CH:22]=[CH:21][O:20]1>>[CH:14]1[C:15]2[CH:16]3[CH:21]([OH:20])[CH:22]([OH:23])[CH:9]([C:10]=2[CH:11]=[CH:12][CH:13]=1)[C:8]1[C:17]3=[CH:18][C:5]2[C:6]([CH:7]=1)=[CH:1][CH:2]=[CH:3][CH:4]=2

참가 물질

3

반응물 2

HCID 7080NaphthaceneHCID 13385Vinylene carbonate

생성물 1

HCID 203759405,12-Dihydro-5,12-ethanobenz[b]anthracene-13,14-diol

실험 절차

A mixture of 7.0 g. of benz[b]anthracene and 26 g. of vinylene carbonate is heated at reflux under nitrogen for 20 hours. The excess vinylene carbonate is removed by vacuum distillation (57° C./9 mm.) and the residue is taken up in 25 ml. of methylene chloride and filtered. The filtrate is treated with twice its volume of methanol and then cooled, producing a tan solid and a mother liquor which is saved. This solid is recrystallized from 60 ml. of 1,2-dichloromethane, collected by filtration, washed with methanol and saved. The mother liquor (saved above) is concentrated giving a gummy solid which is recrystallized from a mixture of methylene chloride and methanol giving a gray solid which is combined with the above solid and recrystallized from ethyl acetate with charcoal treatment giving 5,12-dihydro-5,12-ethanobenz[b]anthracene-13,14-diol, cyclic carbonate as colorless rods. A mixture of 1.3 g. of the cyclic carbonate, 1.05 g. of potassium hydroxide, one ml. of water and 15 ml. of ethanol is stirred at 60°-65° C. for 2 hours. The mixture is diluted with 1-2 volumes of water, filtered and the solid is washed with water and dried giving cis-5,12-dihydro-5,12-ethanobenz[b]anthracene-13,14-diol as a colorless solid. To a solution of 2.6 g. of cis-5,12-dihydro-5,12-ethanobenz[b]anthracene-13,14-diol in 400 ml. of glacial acetic acid at 20° C. is added portionwise 4.4 g. of lead tetraacetate. The reaction is stirred for 45 minutes. The weakly purple colored solid is filtered off, washed with glacial acetic acid and finally water and dried leaving 1.0 g. (m.p. 170°-172° C.) of 5,12-dihydro-5,12-benz[b]anthracene dicarboxaldehyde.

후처리

  1. additionA mixture of 7.0 g
  2. temperatureat reflux under nitrogen for 20 hours
  3. customThe excess vinylene carbonate is removed by vacuum distillation (57° C./9 mm.)
  4. filtrationof methylene chloride and filtered
  5. additionThe filtrate is treated with twice its volume of methanol
  6. temperaturecooled
  7. customproducing a tan solid
  8. customThis solid is recrystallized from 60 ml
  9. filtrationof 1,2-dichloromethane, collected by filtration
  10. washwashed with methanol
  11. concentrationThe mother liquor (saved above) is concentrated
  12. customgiving a gummy solid which
  13. customis recrystallized from a mixture of methylene chloride and methanol giving a gray solid which
  14. customrecrystallized from ethyl acetate with charcoal treatment

출처 및 근거

ORD 기록
ord-803dfb43ee324d4b83f4f403e27e5c32
출처 데이터셋
uspto-grants-1980_02
특허 번호
US04187373

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