(6bS,7S,7aR)-6b-(4-Methoxy-phenyl)-7,7a-dihydro-6bH-cyclopropa[a]acenaphthylene-7-carbaldehyde | 138857-17-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (6bS,7S,7aR)-6b-(4-Methoxy-phenyl)-7,7a-dihydro-6bH-cyclopropa[a]acenaphthylene-7-carbaldehyde
• CAS: 138857-17-7
• 化学式: C₂₁H₁₆O₂
• 分子量: 300.357
• InChiKey: HMOVOKRZKFSNME-SESVDKBCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.06
• 重原子数：
  23.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (6bS,7S,7aR)-6b-(4-Methoxy-phenyl)-7,7a-dihydro-6bH-cyclopropa[a]acenaphthylene-7-carbaldehyde 在 PPA 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以91%的产率得到10-methoxybenzofluoranthene
  参考文献：
  名称：

  Synthesis of anti- and syn- diol epoxides of trans-4,5-dihydro-4,5-dihydroxybenzo[j]fluoranthene and trans-9,10-dihydro-9,10-dihydroxybenzo[j]fluoranthene

  摘要：

  The preparation of diastereomeric anti- and syn-epoxides of benzo[j]fluoranthene (BjF) 4,5- and 9,10-dihydrodiols is described. The anti-diol epoxides were prepared from the corresponding dihydrodiols by epoxidation with m-chloroperoxybenzoic acid. The isomeric syn-diol epoxides were synthesized by base-catalyzed (Amberlyte IRA-400) cyclization of the bromo triol derivatives which in turn were prepared from the respective dihydrodiols by treatment with N-bromoacetamide in aqueous THF. New methods were employed for the preparation of 4- and 10-hydroxyBjF which are precursors for BjF-4,5-dihydrodiol and BjF-9,10-dihydrodiol. Cyclodehydration of 2-[2-(9-methoxy-11-hydroxybenzo[a]fluoren-11-yl)ethyl]-1,3-dioxane in polyphosphoric acid afforded 4-methoxyBjF (from which the phenol is readily prepared) in 87% yield. Reaction of 1-(4-methoxyphenyl)-acenaphthylene with ethyl diazoacetate is catalyzed by copper-bronze and gave a mixture of diastereomeric cyclopropane carboxylates. These were converted to the corresponding aldehydes by diisobutylaluminum hydride reduction and Swern oxidation followed by cyclodehydration with polyphosphoric acid to give 10-methoxyBjF in 91% yield. It had previously been reported that reduction of BjF-4,5-quinone to BjF-4,5-dihydrodiol occurs in low yield due to overreduction to a mixture of tetrahydro diols and triols. We now report that complexation of the quinone with silver nitrate followed by reduction with potassium borohydride in the presence of oxygen affords BjF-4,5-dihydrodiol in 91% yield.

  DOI：

  10.1021/jo00032a034
• 作为产物：
  描述：

  1-(4-甲氧基苯基)苊 在 草酰氯 、 铜 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 作用下， 反应 9.75h， 生成 (6bS,7S,7aR)-6b-(4-Methoxy-phenyl)-7,7a-dihydro-6bH-cyclopropa[a]acenaphthylene-7-carbaldehyde
  参考文献：
  名称：

  Synthesis of anti- and syn- diol epoxides of trans-4,5-dihydro-4,5-dihydroxybenzo[j]fluoranthene and trans-9,10-dihydro-9,10-dihydroxybenzo[j]fluoranthene

  摘要：

  The preparation of diastereomeric anti- and syn-epoxides of benzo[j]fluoranthene (BjF) 4,5- and 9,10-dihydrodiols is described. The anti-diol epoxides were prepared from the corresponding dihydrodiols by epoxidation with m-chloroperoxybenzoic acid. The isomeric syn-diol epoxides were synthesized by base-catalyzed (Amberlyte IRA-400) cyclization of the bromo triol derivatives which in turn were prepared from the respective dihydrodiols by treatment with N-bromoacetamide in aqueous THF. New methods were employed for the preparation of 4- and 10-hydroxyBjF which are precursors for BjF-4,5-dihydrodiol and BjF-9,10-dihydrodiol. Cyclodehydration of 2-[2-(9-methoxy-11-hydroxybenzo[a]fluoren-11-yl)ethyl]-1,3-dioxane in polyphosphoric acid afforded 4-methoxyBjF (from which the phenol is readily prepared) in 87% yield. Reaction of 1-(4-methoxyphenyl)-acenaphthylene with ethyl diazoacetate is catalyzed by copper-bronze and gave a mixture of diastereomeric cyclopropane carboxylates. These were converted to the corresponding aldehydes by diisobutylaluminum hydride reduction and Swern oxidation followed by cyclodehydration with polyphosphoric acid to give 10-methoxyBjF in 91% yield. It had previously been reported that reduction of BjF-4,5-quinone to BjF-4,5-dihydrodiol occurs in low yield due to overreduction to a mixture of tetrahydro diols and triols. We now report that complexation of the quinone with silver nitrate followed by reduction with potassium borohydride in the presence of oxygen affords BjF-4,5-dihydrodiol in 91% yield.

  DOI：

  10.1021/jo00032a034