1-<2-(9-methoxy-11-hydroxybenzofluoren-11-yl)-ethyl>-1,3-dioxane | 138857-14-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 1-<2-(9-methoxy-11-hydroxybenzofluoren-11-yl)-ethyl>-1,3-dioxane
• 英文别名: 11-[2-(1,3-dioxan-2-yl)ethyl]-9-methoxybenzo[a]fluoren-11-ol
• CAS: 138857-14-4
• 化学式: C₂₄H₂₄O₄
• 分子量: 376.452
• InChiKey: MQYTULXNABQPHO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

上下游信息

反应信息

• 作为反应物：
  描述：

  1-<2-(9-methoxy-11-hydroxybenzofluoren-11-yl)-ethyl>-1,3-dioxane 在 PPA 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以87%的产率得到4-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：

  (1,3-dioxan-2-yl)ethylmagnesium bromide 、 9-methoxy-11H-benzofluoren-11-one 以 四氢呋喃 为溶剂， 以93%的产率得到1-<2-(9-methoxy-11-hydroxybenzofluoren-11-yl)-ethyl>-1,3-dioxane
  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

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.