2,7-Bis-triisopropylsilanyloxy-phenanthro[3,4-c]phenanthrene-9,12,13,16-tetraol | 261776-71-0

• 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-Bis-triisopropylsilanyloxy-phenanthro[3,4-c]phenanthrene-9,12,13,16-tetraol
• 英文别名: 6,11-Bis[tri(propan-2-yl)silyloxy]hexahelicene-1,4,13,16-tetrol
• CAS: 261776-71-0
• 化学式: C₄₄H₅₆O₆Si₂
• 分子量: 737.096
• InChiKey: XJTOGMUEXSYVGI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.38
• 重原子数：
  52
• 可旋转键数：
  10
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  99.4
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  甲醇 、 2,7-Bis-triisopropylsilanyloxy-phenanthro[3,4-c]phenanthrene-9,12,13,16-tetraol 在 盐酸 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 2.0h， 以92%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
• 作为产物：
  描述：

  6,11-Bis[tri(propan-2-yl)silyloxy]hexahelicene-1,4,13,16-tetrone 在 sodium dithionite 作用下， 以 二氯甲烷 、 水 、 乙酸乙酯 为溶剂， 反应 1.0h， 生成 2,7-Bis-triisopropylsilanyloxy-phenanthro[3,4-c]phenanthrene-9,12,13,16-tetraol
  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

• Why (1<i>S</i>)-Camphanates Are Excellent Resolving Agents for Helicen-1-ols and Why They Can Be Used to Analyze Absolute Configurations
  作者：Tienthong Thongpanchang、Kamil Paruch、Thomas J. Katz、Arnold L. Rheingold、Kin-Chung Lam、Louise Liable-Sands

  DOI：10.1021/jo9919411

  日期：2000.3.1

  The questions considered in this paper are why, as agents for resolving helicenols, camphanate esters are particularly effective, and why, in all 19 examples studied, when the (1S)-camphanates of(P)- and (M)-helicen-1-ols are chromatographed on silica gel, the former has the lower Rf. Models are proposed for the favored conformations of the esters, and to support the models, evidence is provided from five X-ray diffraction analyses and four ROESY analyses supplemented by molecular mechanics calculations. The essential discovery is that, presumably to avoid a steric interaction between a methyl on the camphanate's bridge and the helicene skeleton, the O=CCO conformation is anti-periplanar in (M)-helicenol camphanates and syn-periplanar in (P)-helicenol camphanates. In the former, the lactone carbonyl points toward the helicene ring system, and in the latter, it points away.
• 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.