trans-4,5-dihydro-4,5-dihydroxybenzofluoranthene | 106542-80-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: trans-4,5-dihydro-4,5-dihydroxybenzofluoranthene
• 英文别名: (14S,15S)-pentacyclo[10.7.1.02,11.03,8.016,20]icosa-1(20),2(11),3,5,7,9,12,16,18-nonaene-14,15-diol
• CAS: 106542-80-7；151258-40-1
• 化学式: C₂₀H₁₄O₂
• 分子量: 286.33
• InChiKey: RRKIIWROEQLDQF-PXNSSMCTSA-N

物化性质

• 熔点：
  >170 °C (decomp)
• 沸点：
  566.6±50.0 °C(Predicted)
• 密度：
  1.43±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-4,5-dihydro-4,5-dihydroxybenzofluoranthene 在 盐酸 、 Amberlite IRA-400 、 N-溴代乙酰胺 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 9.5h， 生成 trans-4,5-dihydroxy-syn-6,6a-epoxy-4,5,6,6a-tetrahydrobenzofluoranthene
  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：

  ethyl 9-methoxy-11H-benzofluorene-11-carboxylate 在 吡啶 、 甲醇 、 sodium hydroxide 、 sodium tetrahydroborate 、 potassium dihydrogenphosphate 、 钾硼氢 、 adogen 464 、 甲烷磺酸 、 potassium nitrososulfonate 、 氨 、 三溴化硼 、 对甲苯磺酸 、 甲基萘 作用下， 以 吡啶 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 苯 为溶剂， 反应 170.67h， 生成 trans-4,5-dihydro-4,5-dihydroxybenzofluoranthene
  参考文献：
  名称：

  Synthesis of the major metabolic dihydro diols of benzo[j]fluoranthene

  摘要：

  DOI：

  10.1021/jo00381a025

文献信息

• 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
  作者：Zhen Min He、Joseph E. Rice、Edmond J. LaVoie

  DOI：10.1021/jo00032a034

  日期：1992.3

  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.
• Synthesis of the major metabolic dihydro diols of benzo[j]fluoranthene
  作者：Joseph E. Rice、Hsien Cheng Shih、Nalband Hussain、Edmond J. LaVoie

  DOI：10.1021/jo00381a025

  日期：1987.3