2,5-bis[pyrrolo(2,4,6-trimethylphenyl)methyl]thiophene | 223921-69-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2,5-bis[pyrrolo(2,4,6-trimethylphenyl)methyl]thiophene
• 英文别名: 5,10-dimesityl-21-thiatripyrrane；5,10-dimesityl-16-thia-5,10,15,17-tetrahydrotripyrrin；5,10-dimesityl-16-thiatripyrrane；2-[[5-[1H-pyrrol-2-yl-(2,4,6-trimethylphenyl)methyl]thiophen-2-yl]-(2,4,6-trimethylphenyl)methyl]-1H-pyrrole
• CAS: 223921-69-5
• 化学式: C₃₂H₃₄N₂S
• 分子量: 478.701
• InChiKey: LTXBGRMJIPMPMB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.3
• 重原子数：
  35
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  59.8
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,5-bis[pyrrolo(2,4,6-trimethylphenyl)methyl]thiophene 在 4 A molecular sieve 、 三氯氧磷 作用下， 以 氯仿 为溶剂， 生成
  参考文献：
  名称：

  Synthesis of pseudoaromatic expanded porphyrin analogues

  摘要：

  Optically active expanded porphyrins bearing thiophene were synthesized by Schiff base forming reaction. The condensation of thiophene containing 1,14-bisformyl tripyrrane with aromatic diamines Failed to give desired macrocycles but condensation with aliphatic 1,2-diamines gave the desired products. The macrocycles synthesized tend to maintain 18 pi system and the ethylene bridge shows somewhat resistance toward oxidation. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00044-1
• 作为产物：
  描述：

  2,4,6-三甲基苯甲醛 、 alkaline earth salt of/the/ methylsulfuric acid 在 正丁基锂 、 四甲基乙二胺 、 三氟化硼乙醚 作用下， 以 正己烷 为溶剂， 反应 2.0h， 生成 2,5-bis[pyrrolo(2,4,6-trimethylphenyl)methyl]thiophene
  参考文献：
  名称：

  Core-modified porphyrins. Part 4: Steric effects on photophysical and biological properties in vitro

  摘要：

  21,23-Dithiaporphyrins (2-10) were designed and prepared as analogues of 5,20-diphenyl-10,15-bis(4-carboxylatomethoxy)phenyl-21,23-dithiaporphyrin (1) to examine the impact of steric bulk at the 5- and 20-meso positions as well as the impact of symmetry. Changes at the meso positions had minimal impact on the UV-vis-near-IR absorption spectra, quantum yields for the generation of singlet oxygen, and quantum yields for fluorescence and some impact on values of the octanol/water partition coefficient. Of the compounds 1-10, 5-phenyl-20-(2-thienyl)-10,15-bis-(4-carboxylatomethoxy-phenyl)-21,23-dithiaporphyrin (3) showed the greatest phototoxicity toward cultured R3230AC cells, with 68% cell kill at 1 x 10(-7) M and irradiation with 5 J cm(-2) of 350-750 nm light. Results in this study suggest that smaller substituents on the meso ring and less symmetrical compounds are more effective as photosensitizers than compounds with two bulky substituents at adjoining meso sites and a higher symmetry. The mitochondria appear to be involved in the process of phototoxicity as determined by the inhibition of whole cell cytochrome c oxidase activity in cells treated with 3 and light. No impact upon mitochondrial cytochrome c oxidase activity was observed in cells treated with 3 and no light. Fluorescence microscopy studies suggest that the mitochondria are not initial sites of accumulation of 3. (c) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2004.12.048

文献信息

• Core-Modified Expanded Porphyrins with Large Third-Order Nonlinear Optical Response
  作者：Harapriya Rath、Jeyaraman Sankar、Viswanathan PrabhuRaja、Tavarekere K. Chandrashekar、Amit Nag、Debabrata Goswami

  DOI：10.1021/ja0537575

  日期：2005.8.24

  The third-order nonlinear optical response through measurement of two-photon absorption cross-sections (TPACS) for aromatic core-modified expanded porphyrin analogues by a femtosecond open aperture Z-scan method is reported. The values reported here are among the largest known so far in the literature for any organic molecules.

  报道了通过飞秒开孔 Z 扫描方法测量芳香核修饰的膨胀卟啉类似物的双光子吸收截面 (TPACS) 的三阶非线性光学响应。此处报告的值是迄今为止所有有机分子文献中已知的最大值之一。
• 30π Aromatic Meso-Substituted Heptaphyrin Isomers:  Syntheses, Characterization, and Spectroscopic Studies
  作者：Venkataramanarao G. Anand、Simi K. Pushpan、S. Venkatraman、Seenichamy Jeyaprakash Narayanan、Abhishek Dey、Tavarekere K. Chandrashekar、Raja Roy、Bhavani S. Joshi、S. Deepa、G. Narahari Sastry

  DOI：10.1021/jo025788d

  日期：2002.9.1

  bithiophene unit or in the tripyrrane unit. Theoretical calculations performed on three different heptaphyrins, 4, 5, and 17, also reveal that the inverted structures are approximately 35-40 kJ lower in energy relative to the corresponding noninverted structures. Furthermore, one of the heptaphyrins 10c shows the presence of two conformers in solution in the ratio 1:2 and no interconversion between the conformers

  报道了通过[5 + 2]或[4 + 3]酸催化的缩合反应和容易获得的和空气稳定的前体的氧化偶联反应合成新的芳香30pi七氢卟啉的方法。遵循的方法学不仅简单有效，而且可以合成一系列在核心中带有不同杂原子的七卟啉。发现修饰的三吡喃11和四吡喃12的氧化偶联反应取决于所用的酸浓度以及内消旋位置上存在的取代基。将11和12中的内消旋芳基取代基更改为内消旋异戊基取代基可得到新的七卟啉18。结构表征已通过广泛的1H和2D NMR研究完成。当杂环的连接改变时，此处报道的七卟啉显示出丰富的结构多样性，因此，已经观察到一个环和两个环倒置。通过明智地选择前体，可以控制联噻吩单元或三吡喃单元中的环反转位点。对三种不同的七卟啉4、5和17进行的理论计算也表明，相对于相应的非反向结构，反向结构的能量降低了约35-40 kJ。此外，一种七卟啉10c在溶液中以1：2的比例显示了两个构象异构体的存在，并且在343-228
• One-Pot Synthesis of Core-Modified Rubyrin, Octaphyrin, and Dodecaphyrin: Characterization and Nonlinear Optical Properties
  作者：Rajeev Kumar、Rajneesh Misra、Tavarekere K. Chandrashekar、Amit Nag、Debabrata Goswami、Eringathodi Suresh、Cherumuttathu H. Suresh

  DOI：10.1002/ejoc.200700466

  日期：2007.9

  Modified 26π rubyrin, 36π octaphyrin, and 54π dodecaphyrin systems have been synthesized in moderately good yields through acid-catalyzed condensations of terthiophene diols and tripyrranes. The product distributions are decided both by the acid catalyst concentration and by the nature of the meso substituents. For example, a new isomer of [26]hexaphyrin(1.1.1.1.0.0) (rubyrin) was obtained with 0.3

  通过三噻吩二醇和三吡喃的酸催化缩合，已经以中等良好的收率合成了改性的 26π 红宝石、36π 八卟啉和 54π 十二烷系统。产物分布由酸催化剂浓度和内消旋取代基的性质决定。例如，获得了 0.3 当量的 [26] 六卟啉 (1.1.1.1.0.0)（红宝石）的新异构体。对甲苯磺酸，当至少一种前体中的内消旋取代基是甲基时。对三噻吩二醇中的对甲氧基取代基的甲基取代基的变化导致形成 [3 + 3 + 3 + 3] 缩合产物 - [54] 十二烷醇 (1.1.1.1.0.0.1.1.1.1.0.0) – 除了预期的红宝石。此外，酸浓度增加到 0.6 当量。导致形成新的 [36] 八茶碱 (1.1.1.1.1.1.0.0)，以及红宝石和十二茶碱。Octphyrin 的单晶 X 射线分析代表了具有 6 个内消旋链的 Octphyrin 平面构象的第一个例子。在红宝石 19 中，与三噻吩亚基相对的一个噻吩环被反转，而在八菲林
• Meso Aryl Heptaphyrins:  The First 30π Aromatic Expanded Porphyrins with an Inverted Structure
  作者：Venkataramana Rao. G. Anand、Simi K. Pushpan、Alagar Srinivasan、Seenichamy Jeyaprakash Narayanan、Bashyam Sridevi、Tavarekere K. Chandrashekar、Raja Roy、Bhavani S. Joshi

  DOI：10.1021/ol000251c

  日期：2000.11.1

  [reaction: see text] Synthesis of new meso aryl 30pi heptaphyrins 2, 3, and 4 is achieved. Spectroscopic studies reveal that 2, 3, and 4 are aromatic and possess an inverted structure.

  [反应：见正文]实现了新的内消旋芳基30pi七卟啉2、3和4的合成。光谱研究表明2、3和4是芳族的并且具有倒置的结构。
• Core modified oxybenziporphyrins: new aromatic ligands for metal–carbon bond activationElectronic supplementary information (ESI) available: See FAB mass, UV-Vis, 1H, 2D NMR spectra. http://www.rsc.org/suppdata/cc/b1/b111155h/
  作者：Sundararaman Venkatraman、Venkataramanarao G. Anand、Simi K. Pushpan、Jeyaraman Sankar、Tavarekere K. Chandrashekar

  DOI：10.1039/b111155h

  日期：2002.2.27

  Successful syntheses of two new aromatic core modified oxybenziporphyrins by a simple ‘3 + 1’ methodology and the first aromatic core modified oxybenziporphyrin palladium complex are reported.

  报告采用简单的 "3 + 1 "方法成功合成了两种新的芳香核修饰氧苯并卟啉，并首次合成了芳香核修饰氧苯并卟啉钯络合物。