2,7,9,16-Tetramethoxy-phenanthro[3,4-c]phenanthrene-12,13-diol | 261914-43-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 2,7,9,16-Tetramethoxy-phenanthro[3,4-c]phenanthrene-12,13-diol
• 英文别名: 4,6,11,13-tetramethoxyhexahelicene-1,16-diol
• CAS: 261914-43-6
• 化学式: C₃₀H₂₄O₆
• 分子量: 480.517
• InChiKey: FUHCLHVJPPMNKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  36
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,7,9,16-Tetramethoxy-phenanthro[3,4-c]phenanthrene-12,13-diol 在 盐酸 、 4-二甲氨基吡啶 、 氢氧化钾 、 三乙胺 作用下， 以 乙醇 、 1,2-二氯乙烷 为溶剂， 反应 6.0h， 生成 4,6,11,13-Tetradodecoxyhexahelicene-1,16-diol
  参考文献：
  名称：

  Acidified Alcohols as Agents to Introduce and Exchange Alkoxyls on the Periphery of Helicenes

  摘要：

  Alcohols containing HCl transform the hydroquinone reduction-products of helicenebisquinones into p-alkoxyphenols that have the alkoxyls specifically on the peripheries of the helices. The reactions are quick, and the yields are high. Alkoxyls at the 6-position are replaced also, but only after 2 h at 60 degrees C, not after the 5 min at 25 degrees C sufficient to replace the peripheral hydroxyls of the hydroquinones. After the remaining inside hydroxyls of a dihydroxytetramethoxy[6]helicene prepared by this procedure have been converted into camphanates, one diastereomer crystallizes from solution, allowing an enantiomer resolution to be carried out on a large scale. By then simply reapplying the procedure with alcoholic acid, a variety of resolved dihydroxytetraalkoxy[6]helicenes can be prepared in excellent yields without resolution procedures having to be developed for each, Similar procedures are effective when applied to a [7]carbohelicene.

  DOI：

  10.1021/jo9914972
• 作为产物：
  描述：

  [4,6,11,13-tetramethoxy-16-[(1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carbonyl]oxyhexahelicen-1-yl] (1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carboxylate 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以99%的产率得到2,7,9,16-Tetramethoxy-phenanthro[3,4-c]phenanthrene-12,13-diol
  参考文献：
  名称：

  Acidified Alcohols as Agents to Introduce and Exchange Alkoxyls on the Periphery of Helicenes

  摘要：

  Alcohols containing HCl transform the hydroquinone reduction-products of helicenebisquinones into p-alkoxyphenols that have the alkoxyls specifically on the peripheries of the helices. The reactions are quick, and the yields are high. Alkoxyls at the 6-position are replaced also, but only after 2 h at 60 degrees C, not after the 5 min at 25 degrees C sufficient to replace the peripheral hydroxyls of the hydroquinones. After the remaining inside hydroxyls of a dihydroxytetramethoxy[6]helicene prepared by this procedure have been converted into camphanates, one diastereomer crystallizes from solution, allowing an enantiomer resolution to be carried out on a large scale. By then simply reapplying the procedure with alcoholic acid, a variety of resolved dihydroxytetraalkoxy[6]helicenes can be prepared in excellent yields without resolution procedures having to be developed for each, Similar procedures are effective when applied to a [7]carbohelicene.

  DOI：

  10.1021/jo9914972

文献信息

• Functionalizations of [6]- and [7]Helicenes at Their Most Sterically Hindered Positions
  作者：Kamil Paruch、Libor Vyklický、David Zhigang Wang、Thomas J. Katz、Christopher Incarvito、Lev Zakharov、Arnold L. Rheingold

  DOI：10.1021/jo035057t

  日期：2003.10.1

  transformed into other functional groups (including phosphine oxides and acetylenes), the ether functions adjacent to these functional groups can then be removed, and the phenols can be oxidized to quinone-acetals. An alternative way to introduce functional groups next to the phenols is to rearrange their phosphate esters. Two reactions that differentiate the ends of the helicenes are also described.

  尽管芳基甲基酮的烯醇醚与苯醌的反应使制备非外消旋的螺旋烯容易，该非外消旋的螺旋烯在其1，ω-位被羟基取代，但是羟基不能促进亲电子引入它们。然而，似乎是由于在6位上的烷氧基被活化，以这种方式制备的[6]-和[7]螺旋醇的醚与亲电试剂结合，将溴和酰基精确地引入这些位置。此外，可以将这些溴和酰基转化为其他官能团（包括氧化膦和乙炔），然后可以除去与这些官能团相邻的醚官能团，并且可以将酚氧化为醌-缩醛。在酚旁边引入官能团的另一种方法是重新排列其磷酸酯。还描述了区分螺旋末端的两个反应。
• Acidified Alcohols as Agents to Introduce and Exchange Alkoxyls on the Periphery of Helicenes
  作者：Spencer D. Dreher、Kamil Paruch、Thomas J. Katz

  DOI：10.1021/jo9914972

  日期：2000.2.1

  Alcohols containing HCl transform the hydroquinone reduction-products of helicenebisquinones into p-alkoxyphenols that have the alkoxyls specifically on the peripheries of the helices. The reactions are quick, and the yields are high. Alkoxyls at the 6-position are replaced also, but only after 2 h at 60 degrees C, not after the 5 min at 25 degrees C sufficient to replace the peripheral hydroxyls of the hydroquinones. After the remaining inside hydroxyls of a dihydroxytetramethoxy[6]helicene prepared by this procedure have been converted into camphanates, one diastereomer crystallizes from solution, allowing an enantiomer resolution to be carried out on a large scale. By then simply reapplying the procedure with alcoholic acid, a variety of resolved dihydroxytetraalkoxy[6]helicenes can be prepared in excellent yields without resolution procedures having to be developed for each, Similar procedures are effective when applied to a [7]carbohelicene.