trans-9,10,dihydro-9,10-dihydroxybenzofluoranthene | 76479-14-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: trans-9,10,dihydro-9,10-dihydroxybenzofluoranthene
• 英文别名: trans-9,10-dihydro-9,10-dihydroxybenzofluoranthene；trans-9,10-dihydro-9,10-dihydroxybenzo[j]fluoranthene；trans-Benzo(j)fluoranthene-9,10-diol；(6S,7S)-pentacyclo[10.7.1.02,11.03,8.016,20]icosa-1(19),2(11),3(8),4,9,12,14,16(20),17-nonaene-6,7-diol
• CAS: 76479-14-6
• 化学式: C₂₀H₁₄O₂
• 分子量: 286.33
• InChiKey: LTGGAYWYOQVIEE-PXNSSMCTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 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-9,10,dihydro-9,10-dihydroxybenzofluoranthene 在 盐酸 、 N-溴代乙酰胺 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 0.5h， 以98%的产率得到r-11-bromo-t-9,c-10,t-12-trihydroxy-9,10,11,12-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：

  7-甲基荧蒽 在 氢氧化钾 、 N-溴代丁二酰亚胺(NBS) 、 lithium aluminium tetrahydride 、 三氯化铝 、 氯化亚砜 、 过氧化氢苯甲酰 、 硫酸 、 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile 、 1,5-二氮杂双环[4.3.0]壬-5-烯 、 双氧水 、 碘 、 sodium methylate 、 silver nitrate 、 pyridinium chlorochromate 、 diborane(6) 作用下， 以 四氢呋喃 、 甲醇 、 二硫化碳 、 四氯化碳 、 乙醚 、 乙醇 、 二氯甲烷 、 水 、 溶剂黄146 、 苯 为溶剂， 反应 59.5h， 生成 trans-9,10,dihydro-9,10-dihydroxybenzofluoranthene
  参考文献：
  名称：

  Study of chemical carcinogenesis. 22. Synthesis of dihydro diols as potential proximate carcinogens of benzofluoranthenes

  摘要：

  DOI：

  10.1021/jo00325a028

文献信息

• 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
• 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.
• Study of chemical carcinogenesis. 22. Synthesis of dihydro diols as potential proximate carcinogens of benzofluoranthenes
  作者：Shantilal Amin、Victoria Bedenko、Edmond LaVoie、Stephen S. Hecht、Dietrich Hoffmann

  DOI：10.1021/jo00325a028

  日期：1981.6