o,p,p,o,p,p,o,p,p-nonaphenylene | 23850-49-9

• 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: o,p,p,o,p,p,o,p,p-nonaphenylene
• CAS: 23850-49-9
• 化学式: C₅₄H₃₆
• 分子量: 684.88
• InChiKey: QJGSHVMSNTXKNG-RFYQFDANSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.44
• 重原子数：
  54.0
• 可旋转键数：
  0.0
• 环数：
  19.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  silver trifluoroacetate 、 o,p,p,o,p,p,o,p,p-nonaphenylene 以 氘代氯仿 为溶剂， 生成
  参考文献：
  名称：

  Synthesis of Nonaphenylenes and Dodecaphenylenes Using Electron-transfer Oxidation of Lipshutz Cuprate Intermediates

  摘要：

  利用电子转移氧化法合成了壬基苯及其六烷基衍生物。在四氢呋喃中氧化由二溴邻三联苯衍生的利普舒茨铜酸盐，可生成九亚苯基，收率适中；而在乙醚中氧化由二碘二乙基邻三联苯衍生的利普舒茨铜酸盐，可生成相应的九亚苯基和十二亚苯基。此外，由二碘二丁基邻三联苯衍生的 Lipshutz 铜酸盐氧化反应只能得到壬烯。

  DOI：

  10.1246/cl.2005.1474
• 作为产物：
  描述：

  2,2''-diamino-m-terphenyl 在 copper(I) bromide 、 氢溴酸 、 magnesium 、 copper dichloride 、 sodium nitrite 作用下， 反应 13.0h， 生成 o,p,p,o,p,p,o,p,p-nonaphenylene
  参考文献：
  名称：

  Syntheses and Physical Properties of Several Polyphenylenes Containing Mixed Linkages

  摘要：

  合成了十四种宏环聚苯烯，包括以下十种新化合物，这些化合物是通过二格里尼亚试剂的分子内或分子间同聚合以及两种二格里尼亚试剂与氯化铜（II）交叉偶联反应合成的：m,m,o,p,o-五苯烯；o,o,p,o,o,p-、m,o,p,m,o,p-、o,p,o,p,o,p-、m,o,p,o,p,o-、m,o,m,o,m,o-、和m,m,m,o,m,o-六苯烯；m,o,p,p,o,m,p-和m,m,m,m,p,o,p-七苯烯；以及m,o,o,m,o,o,m,o,o,m,o,o-十二苯烯。聚苯烯的1H NMR光谱与其开链类似物相比，提供了构成苯环的非平面空间关系的有价值信息。含有p-苯环的化合物的紫外光谱表明，在约260 nm以上K带缺失或强度下降，或该带明显偏移，提供了有用的构象信息。对十二种聚苯烯的最长期波长吸收带进行了经验Hückel分子轨道计算。这些计算为根据光谱数据和Dreiding立体模型推导的构象方面提供了额外的依据。红外光谱表明，在700 cm−1附近缺乏强带一般可以视为缺乏m-苯环的宏环结构的一个合理证据。同时还讨论了聚苯烯在电子轰击下的稳定性。

  DOI：

  10.1246/bcsj.57.3494

文献信息

• Synthesis of Nonaphenylenes and Dodecaphenylenes Using Electron-Transfer Oxidation of Lipshutz Cuprates and Formation of Nanostructural Materials from Hexadodecyloxynonaphenylene
  作者：M. Jalilur Rahman、Jun Yamakawa、Aoi Matsumoto、Hideo Enozawa、Tohru Nishinaga、Kenji Kamada、Masahiko Iyoda

  DOI：10.1021/jo800787u

  日期：2008.7.1

  Nonaphenylenes and dodecaphenylenes have been synthesized by using electron-transfer oxidation of Lipshutz cuprates with duroquinone. Oxidation of the Lipshutz cuprate derived from 4,4"-dibromo-o-terphenyl 3a in THF produced nonaphenylene la in 46% yield, whereas the similar oxidation of the Lipshutz cuprates derived from 4,4"-diiodo-4',5'-dialkyl-o-terphenyls 3b-d in ether afforded the corresponding nonaphenylenes 1b-d and dodecaphenylenes. 2b-d in moderate total yields. In the case of 4,4"-diiodo-4',5'-didodecyloxy-o-terphenyl 3e as the starting material, oxidation of the corresponding Lipshutz cuprate in ether or THF only led to the formation of nonaphenylene le. Both nonaphenylenes 1a-e and dodecaphenylenes 2b-d are unreactive to fight, atmospheric oxygen, and prolonged heating. These oligophenylenes showed strong UV absorption and fluorescent emission and exhibited some redox properties on CV analysis. Moreover, hexadodecyloxyrionaphenylene le exhibits different nanostructures on the surface and in solution to form a film by casting a solution of 1e in cyclohexane, benzene, chloroform, THF, or diisopropyl ether (EPE) and nanofibers from IPE-MeOH (1: 1), indicating different absorption and emission spectra and XRD patterns. The absorption maxima of THF solution, fiber, and film are in the order of le film (315 nm) > fiber (302 nm) > solution (295 ran), whereas the emission maxima are in the order of 1e fiber (425 m) > solution (418 nm) > film (401 nm). XRD analysis revealed that le aligns laterally on a glass or silicon surface to form a thin film with a lamella structure; however, it forms a nanofiber with a Lego-like stacking structure without pi-pi stacking interaction of the aromatic rings. Reflecting the different nanostructures of the 1e film and fiber, a spin-coated le film is found to be effective in detecting the vapor of explosives due to the intercalation of nitroaromatics to the cracked surface of the loosely stacked 1e. In contrast, the 1e fiber is not effective in detection of nitroaromatics but exhibits fluorescence anisotropy. The maximum fluorescence intensity is obtained in a direction perpendicular to the logitudinal axis of the fiber, indicating the stacking direction to be parallel to the longitudinal axis of the fiber.