8-Chlorocarbonyl-1,12-dimethyl-benzo[c]phenanthrene-5-carboxylic acid methyl ester

• 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: 8-Chlorocarbonyl-1,12-dimethyl-benzo[c]phenanthrene-5-carboxylic acid methyl ester
• 英文别名: Methyl 5-carbonochloridoyl-1,12-dimethylbenzo[c]phenanthrene-8-carboxylate；methyl 5-carbonochloridoyl-1,12-dimethylbenzo[c]phenanthrene-8-carboxylate
• 化学式: C₂₃H₁₇ClO₃
• 分子量: 376.839
• InChiKey: DMVDNYHVVZAMNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  8-Chlorocarbonyl-1,12-dimethyl-benzo[c]phenanthrene-5-carboxylic acid methyl ester 在 甲醇 、 lithium hydroxide 、 氯化亚砜 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 (P)-1,12-dimethylbenzo[c]phenanthrene-5,8-dicarboxylic acid chloride
  参考文献：
  名称：

  A Building Block Method for the Synthesis of Higher Cycloamides

  摘要：

  Series of cyclic amides containing optically active helicene, (P)-1, 12-dimethylbenzo[c]phenanthrene, are synthesized using a building block method. The building block consists of one (P)-helicene unit and one dianiline unit with its amino-terminal-protected with benzyloxycarbonyl and its acid terminal activated as acid chloride. The coupling with (P,P....)-[(n - 3) + (n - 2)]diamine followed by deprotection gives (P,P....)-[(n - 1) + n]diamine, which possesses n - 1 parts of (P)-helicene and n parts of dianiline. Cyclization of the (PP....)-[(n - 1) + n]diamine with helicenediacid dichloride gives (P,P....)-[n + n]cycloamide. All the members of (P,P)-[2 + 2]cycloamide to (P,P,P,P,P,P,P,P,P,P)-[10 + 10]cycloamide are synthesized using this method, and are compared spectroscopically.

  DOI：

  10.1021/jo0013047
• 作为产物：
  描述：

  (P)-8-methoxycarbonyl-1,12-dimethylbenzo[c]phenanthrene-5-carboxylic acid 在 氯化亚砜 作用下， 反应 3.0h， 生成 8-Chlorocarbonyl-1,12-dimethyl-benzo[c]phenanthrene-5-carboxylic acid methyl ester
  参考文献：
  名称：

  光学活性1,12-二甲基苯并[ c ]菲-5,8-二酰胺的合成，单层行为及手性朗缪尔-布洛杰特膜的形成

  摘要：

  我们以前曾报道过，由螺旋手性1,12-二甲基苯并[ c ]菲-5，8-二羧酸组成的旋光环状酰胺在水表面形成稳定的单层，并且该单层可以转移到固体载体上得到光学活性的朗缪尔-布洛杰特（LB）膜。在这项研究中，合成了几种相关的酰胺，并对其单层行为进行了研究，以期制备具有官能团的光学活性LB膜。结果表明，环状酰胺结构和环己基部分对于在水表面形成稳定的单分子层至关重要。仲酰胺的N-烷基化不会严重影响单层的形成，而手性LB膜可通过N，N获得环酰胺的-双（3-巯基丙基）衍生物。

  DOI：

  10.1016/s0040-4020(99)00969-2

文献信息

• Synthesis of Helicenediamine Oligomers and Their Formation of Multilayer Structures in Aqueous Solvents
  作者：Jun Mizukami、Hiroki Sugiura、Masahiko Yamaguchi、Kumiko Mushiake

  DOI：10.1246/bcsj.79.317

  日期：2006.2

  Optically active polyamine oligomers containing three to six (P)-5,8-bis(aminomethyl)-1,12-dimethylbenzo[c]phenanthrenes were synthesized employing the two-directional chain extension method. It was critical for the effective coupling of amines and aldehydes to precipitate imine intermediates using the appropriate solvents. UV, CD, fluorescent, and NMR spectroscopic studies revealed that the above-mentioned oligomers form multilayer structures in aqueous solvents, while they form random coil structures in methanol. Such layer structures contained helicene dyads with an anti-conformation in which the BC-rings of helicenes were stacked on each other, and 1,12-dimethyl groups were arranged in the opposite direction. A diastereomeric trimer was also synthesized, the layer structure of which was different from that of the parent trimer. The stereochemistry of the helicene moiety influenced the layer structure.

  采用双向链延伸方法合成了含有三至六个 (P)-5,8- 双（氨基甲基）-1,12-二甲基苯并[c]菲的光学活性多胺低聚物。使用适当的溶剂沉淀亚胺中间体对于胺和醛的有效偶联至关重要。紫外光谱、CD 光谱、荧光光谱和核磁共振光谱研究表明，上述低聚物在水性溶剂中形成多层结构，而在甲醇中则形成无规线圈结构。这种层状结构包含具有反构型的螺旋烯二元体，其中螺旋烯的 BC 环相互堆叠，1,12-二甲基基团的排列方向相反。此外，还合成了一种非对映三聚体，其层结构与母体三聚体不同。螺旋烯分子的立体化学结构影响了层结构。
• Equilibrium shift induced by chiral nanoparticle precipitation in rhodium-catalyzed disulfide exchange reaction
  作者：Masamichi Miyagawa、Mieko Arisawa、Masahiko Yamaguchi

  DOI：10.1016/j.tet.2015.05.106

  日期：2015.7

  Chiral silica (P)-nanoparticles grafted with (P)-helicene recognize the molecular structure of a chiral diol disulfide in the presence of monool disulfide and dibutyl disulfide. The (P)-nanoparticles selectively adsorb the diol disulfide, aggregate, and precipitate from solution. Under rhodium-catalyzed equilibrium among three disulfides, the diol disulfide is removed from solution by precipitation, which induces an equilibrium shift in the solution. By conducting the precipitation experiment twice, we obtained the dial disulfide in 37% yield from a statistical 1:2:1 equilibrium mixture of three disulfides. The method is applied to a racemic monool disulfide, and an optically active dial disulfide is obtained via kinetic resolution and equilibrium shift. (C) 2015 Elsevier Ltd. All rights reserved.
• Optical Resolution of Aromatic Alcohols Using Silica Nanoparticles Grafted with Helicene
  作者：Wataru Ichinose、Masamichi Miyagawa、Zengjian An、Masahiko Yamaguchi

  DOI：10.1021/ol301206r

  日期：2012.6.15

  Optically active silica nanoparticles, with a 70-nm diameter, grafted with (P)-1,12-dimethyl-8-methoxycarbonylbenzo[c]phenanthrene-5-carboxyamide were synthesized, and their use in the kinetic resolution of aromatic alcohols was examined. Up to 61% ee for (S)-2,2-dimethyl-1-phenyl-1-propanol was obtained by a preferential precipitation of aggregates formed with (P)-nanoparticles.
• Synthesis and monolayer behaviors of optically active 1,12- dimethylbenzo[c]phenanthrene-5,8-diamides and the formation of chiral langmuir-blodgett films
  作者：Hitoshi Okubo、Fei Feng、Daisuke Nakano、Tomokazu Hirata、Masahiko Yamaguchi、Tokuji Miyashita

  DOI：10.1016/s0040-4020(99)00969-2

  日期：1999.12

  previously reported that an optically active cyclic amide consisting of a helical chiral 1,12-dimethylbenzo[c]phenanthrene-5, 8-dicarboxylic acid forms a stable monolayer on the water surface, and that the monolayer can be transferred on a solid support giving optically active Langmuir-Blodgett (LB) films. In this study, several related amides were synthesized, and their monolayer behaviors were investigated

  我们以前曾报道过，由螺旋手性1,12-二甲基苯并[ c ]菲-5，8-二羧酸组成的旋光环状酰胺在水表面形成稳定的单层，并且该单层可以转移到固体载体上得到光学活性的朗缪尔-布洛杰特（LB）膜。在这项研究中，合成了几种相关的酰胺，并对其单层行为进行了研究，以期制备具有官能团的光学活性LB膜。结果表明，环状酰胺结构和环己基部分对于在水表面形成稳定的单分子层至关重要。仲酰胺的N-烷基化不会严重影响单层的形成，而手性LB膜可通过N，N获得环酰胺的-双（3-巯基丙基）衍生物。
• A Building Block Method for the Synthesis of Higher Cycloamides
  作者：Hitoshi Okubo、Masahiko Yamaguchi

  DOI：10.1021/jo0013047

  日期：2001.2.1

  Series of cyclic amides containing optically active helicene, (P)-1, 12-dimethylbenzo[c]phenanthrene, are synthesized using a building block method. The building block consists of one (P)-helicene unit and one dianiline unit with its amino-terminal-protected with benzyloxycarbonyl and its acid terminal activated as acid chloride. The coupling with (P,P....)-[(n - 3) + (n - 2)]diamine followed by deprotection gives (P,P....)-[(n - 1) + n]diamine, which possesses n - 1 parts of (P)-helicene and n parts of dianiline. Cyclization of the (PP....)-[(n - 1) + n]diamine with helicenediacid dichloride gives (P,P....)-[n + n]cycloamide. All the members of (P,P)-[2 + 2]cycloamide to (P,P,P,P,P,P,P,P,P,P)-[10 + 10]cycloamide are synthesized using this method, and are compared spectroscopically.