(P)-8-methoxycarbonyl-1,12-dimethylbenzo[c]phenanthrene-5-carboxylic acid

• 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: (P)-8-methoxycarbonyl-1,12-dimethylbenzo[c]phenanthrene-5-carboxylic acid
• 英文别名: (P)-1,12-dimethyl-8-methoxycarbonylbenzo[c]phenanthrene-5-carboxylic acid；5-methoxycarbonyl-1,12-dimethylbenzo[c]phenanthrene-8-carboxylic acid
• 化学式: C₂₃H₁₈O₄
• 分子量: 358.394
• InChiKey: ANFUANMOOXIKGP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 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：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (P)-8-methoxycarbonyl-1,12-dimethylbenzo[c]phenanthrene-5-carboxylic acid 在 palladium on activated charcoal 盐酸 、 4-二甲氨基吡啶 、 sodium hydroxide 、 sodium tetrahydroborate 、 氯化亚砜 、 sodium azide 、 氨 、 氢气 、 phosphorus pentoxide 、 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 35.17h， 生成 5-{8-(t-butoxycarbonylaminomethyl)-1,12-dimethylbenzo[c]phenanthrene-5-yl}methylaminomethyl-8-(t-butoxycarbonylaminomethyl)-1,12-dimethylbenzo[c]phenanthrene
  参考文献：
  名称：

  Synthesis of Helicenediamine Oligomers and Their Formation of Multilayer Structures in Aqueous Solvents

  摘要：

  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。

  DOI：

  10.1246/bcsj.79.317
• 作为产物：
  描述：

  dimethyl (P)-1,12-dimethylbenzo[c]phenanthrene-5,8-dicarboxylate 在 barium dihydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 48.0h， 以89%的产率得到(P)-8-methoxycarbonyl-1,12-dimethylbenzo[c]phenanthrene-5-carboxylic acid
  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

文献信息

• 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。
• Synthesis and Thermally Stable Helix-Dimer Formation of Amidohelicene Oligomers
  作者：Ryo Amemiya、Wataru Ichinose、Masahiko Yamaguchi

  DOI：10.1246/bcsj.20100041

  日期：2010.7.15

  dimer and the higher homologs, and vapor pressure osmometry studies revealed the formation of dimeric aggregates for the latter. It is noted that amidohelicene oligomers possessing two-atom linking groups between helicene and m-phenylene spacer formed helix-dimers in solution as were ethynylhelicene oligomers. The helix-dimer of the amidohelicene octamer in chloroform was very stable, and did not dissociate

  通过双向方法以高产率合成了旋光酰胺螺旋单体到九聚体。氯仿中的 CD 光谱表现出二聚体和更高同系物之间的巨大差异，蒸汽压渗透法研究表明后者形成了二聚体聚集体。注意到在螺旋烯和间亚苯基间隔基之间具有两个原子连接基团的酰胺螺旋低聚物在溶液中形成螺旋二聚体，正如乙炔基螺旋低聚物一样。氯仿中酰胺螺旋八聚体的螺旋二聚体非常稳定，加热至 60 °C 时不会在 5 x 10-8 M 下解离。在氢键断裂溶剂、DMSO 或 THF 中，酰胺螺旋低聚物解离为无规卷曲状态。通过改变氯仿和 DMSO 混合溶剂的比例，螺旋二聚体和无规螺旋之间的平衡发生了变化。值得注意的是，对于螺旋二聚体和无规螺旋的各种混合物，平衡不受温度的影响。因此，酰胺-和乙炔基螺旋烯低聚物对环境的敏感性是完全不同的。
• Reversible Aggregation and Deaggregation of Helicene-grafted Chiral Silica Nanoparticles Induced by Aromatic Solvents
  作者：Zengjian An、Yoshizumi Yasui、Takanari Togashi、Tadafumi Adschiri、Shunpei Hitosugi、Hiroyuki Isobe、Takeshi Higuchi、Masatsugu Shimomura、Masahiko Yamaguchi

  DOI：10.1246/cl.2010.1004

  日期：2010.9.5

  Silica nanoparticles with sizes of 210 and 440 nm were grafted with (P)- or (M)-1,12-dimethylbenzo[c]phenanthrenes by silane coupling with helicenamidated (3-aminopropyl)trimethoxysilane. The chiral nanoparticles deaggregated and aggregated with sonication in soft and hard aromatic solvents.

  通过硅烷偶联(3-氨基丙基)三甲氧基硅烷，用(P)-或(M)-1,12-二甲基苯并[c]菲接枝了尺寸为 210 纳米和 440 纳米的二氧化硅纳米粒子。手性纳米粒子在软性和硬性芳香溶剂中经超声处理后会发生解聚和聚集。
• Chiral recognition in aggregation of gold nanoparticles grafted with helicenes
  作者：Zengjian An、Masahiko Yamaguchi

  DOI：10.1039/c2cc32735j

  日期：——

  Chiral recognition was observed in the interactions of gold nanoparticles grafted with (±)-, (M)-, and (P)-helicenethiol. Although the nanoparticles contain equal enantiomeric excess, a 1 : 1 mixture of (M)- and (P)-nanoparticles aggregated more rapidly in solution than (±)-nanoparticles.

  在嫁接有（±）-、（M）-和（P）-螺旋烯硫醇的金纳米颗粒的相互作用中观察到了手性识别。尽管纳米颗粒包含等量的对映体，但（M）-和（P）-纳米颗粒的1：1混合物在溶液中的聚集速度比（±）-纳米颗粒更快。
• 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。