36,37,38,39,40-Pentamethoxy-2,9,16,23,30-pentazahexacyclo[30.3.1.14,8.111,15.118,22.125,29]tetraconta-1(35),2,4(40),5,7,9,11(39),12,14,16,18(38),19,21,23,25(37),26,28,30,32(36),33-icosaene-3,10,17,24,31-pentol | 1068432-37-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 36,37,38,39,40-Pentamethoxy-2,9,16,23,30-pentazahexacyclo[30.3.1.14,8.111,15.118,22.125,29]tetraconta-1(35),2,4(40),5,7,9,11(39),12,14,16,18(38),19,21,23,25(37),26,28,30,32(36),33-icosaene-3,10,17,24,31-pentol
• 英文别名: 36,37,38,39,40-pentamethoxy-2,9,16,23,30-pentazahexacyclo[30.3.1.14,8.111,15.118,22.125,29]tetraconta-1(35),2,4(40),5,7,9,11(39),12,14,16,18(38),19,21,23,25(37),26,28,30,32(36),33-icosaene-3,10,17,24,31-pentol
• CAS: 1068432-37-0
• 化学式: C₄₀H₃₅N₅O₁₀
• 分子量: 745.745
• InChiKey: PMGPZQHEDMEMDP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  55
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  192
• 氢给体数：
  5
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  36,37,38,39,40-Pentamethoxy-2,9,16,23,30-pentazahexacyclo[30.3.1.14,8.111,15.118,22.125,29]tetraconta-1(35),2,4(40),5,7,9,11(39),12,14,16,18(38),19,21,23,25(37),26,28,30,32(36),33-icosaene-3,10,17,24,31-pentol 、 四丁基溴化铵 以 氯仿 为溶剂， 反应 12.0h， 以84%的产率得到Tetrabutylazanium;37,38,39,40-tetramethoxy-3,10,17,24,31-pentaoxo-2,9,16,23,30-pentazahexacyclo[30.3.1.14,8.111,15.118,22.125,29]tetraconta-1(35),4(40),5,7,11(39),12,14,18(38),19,21,25(37),26,28,32(36),33-pentadecaen-36-olate
  参考文献：
  名称：

  Folding-Promoted TBACl-Mediated Chemo- and Regioselective Demethylations of Methoxybenzene-Based Macrocyclic Pentamers

  摘要：

  Tetrabutylammonium chloride (TBACI) salt alone has not been shown previously to be capable of removing methoxy groups. It is demonstrated here that the use of TBACI achieves efficient folding-promoted chemo- and regioselective demethylations, eliminating up to two out of five methyl groups situated in similar macrocyclic chemical microenvironments.

  DOI：

  10.1021/ol202658p
• 作为产物：
  描述：

  3-氨基-2-甲氧基苯甲酸 在 三氯氧磷 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 12.17h， 以46%的产率得到36,37,38,39,40-Pentamethoxy-2,9,16,23,30-pentazahexacyclo[30.3.1.14,8.111,15.118,22.125,29]tetraconta-1(35),2,4(40),5,7,9,11(39),12,14,16,18(38),19,21,23,25(37),26,28,30,32(36),33-icosaene-3,10,17,24,31-pentol
  参考文献：
  名称：

  围绕周边可变功能化的混合大环五聚体的一锅合成

  摘要：

  一锅大环化而不是四或六个残基的大环，可以高度选择性地形成通过分子内氢键刚性化的五残基的大环。通过使单体与带有不同外部侧链的高级低聚物反应，可以实现五聚体周围的可变功能化。这些杂化五聚体的形成表明一锅大环化的链增长机理，其中单体连续添加到高级低聚物上的速度比两个单体或两个高级低聚物之间的速度快。

  DOI：

  10.1021/ol200538d

文献信息

• Highly selective one-pot synthesis of H-bonded pentagon-shaped circular aromatic pentamers
  作者：Bo Qin、Wei Qiang Ong、Ruijuan Ye、Zhiyun Du、Xiuying Chen、Yan Yan、Kun Zhang、Haibin Su、Huaqiang Zeng

  DOI：10.1039/c0cc05791f

  日期：——

  One-pot, multi-molecular macrocyclization allows the highly selective preparation of pentagon-shaped circular aromatic pentamers mediated by an inward-pointing continuous hydrogen-bonding network.

  一锅法多分子大环化反应可通过内向连续氢键网络介导高选择性制备五边形环形芳香五聚体。
• POCl3-mediated H-bonding-directed one-pot synthesis of macrocyclic pentamers, strained hexamers and highly strained heptamers
  作者：Ying Liu、Bo Qin、HuaQiang Zeng

  DOI：10.1007/s11426-011-4438-0

  日期：2012.1

  the basis of bimolecular reactions between two oligomers higher than monomers via kinetic simulations. In this scenario, the acyclic pentamer is kinetically “trapped” to undergo an intramolecular cyclization to yield circular pentamer, rather than to produce acyclic hexamer. As a result, acyclic hexamer precursor is generated largely from sterically demanding bimolecular reactions between a dimer and

  先前我们已经证明POCl 3介导的H键导向的一锅大环化可以高度选择性地制备五残基大环，将其作为主要产物，六聚体的产率低，并且四聚体和七聚体均不可检测。在这些4-7个残基大环中，用乙基取代内部排列的甲基，从而改变了它们之间的相对稳定性顺序。具体而言，乙氧基取代的六残基大环而不是五聚体在计算上被证明是最稳定的，这表明含乙氧基的六聚体可能在合适的条件下形成为主要产物。我们通过改变反应温度和浓度来研究这种可能性，始终提供五聚体作为主要的大环化合物，并产生大量的应变环状六聚体和高度应变环状七聚体。可以通过动力学模拟基于高于单体的两种低聚物之间的双分子反应来合理解释这种差异。在这种情况下，无环五聚体在动力学上被“捕获”以进行分子内环化，生成环状五聚体，而不是产生无环六聚体。结果，无环六聚体前体主要是由二聚体和四聚体之间，或动力学上比产生五聚体的链增长反应慢的两个三聚体之间的空间要求性双分子反应产生的。
• One-Pot Multimolecular Macrocyclization for the Expedient Synthesis of Macrocyclic Aromatic Pentamers by a Chain Growth Mechanism
  作者：Bo Qin、Sheng Shen、Chang Sun、Zhiyun Du、Kun Zhang、Huaqiang Zeng

  DOI：10.1002/asia.201100409

  日期：2011.12.2

  POCl3‐mediated one‐pot macrocyclization allows the highly selective formation of five‐residue macrocycles that are rigidified by internally placed intramolecular hydrogen bonds. Mechanistic investigation by using tailored competition experiments and kinetic simulation provides a comprehensive model, supporting a chain‐growth mechanism underlying the one‐pot formation of aromatic pentamers, whereby the successive

  POCl 3介导的一锅大环化可以高度选择性地形成五个残基的大环，这些大环通过内部放置的分子内氢键而得以硬化。通过使用量身定制的竞争实验和动力学模拟进行的机理研究，提供了一个全面的模型，支持了芳香五聚体一锅形成基础上的链增长机理，从而将双官能单体单元相继添加到另一种单体或增长的低聚主链上比其他类型的涉及低聚物的双分子缩合要快，其长于单体。D3在B3LYP / 6‐31G *级别的DFT计算表明，相对于替代的四，六和七残基大循环，五残基五聚体是最稳定的。
• Crystallographic Evidence of an Unusual, Pentagon-Shaped Folding Pattern in a Circular Aromatic Pentamer
  作者：Bo Qin、Xiuying Chen、Xiao Fang、Yingying Shu、Yeow Kwan Yip、Yan Yan、Siyan Pan、Wei Qiang Ong、Changliang Ren、Haibin Su、Huaqiang Zeng

  DOI：10.1021/ol801980h

  日期：2008.11.20

  Introduction of a continuous hydrogen-bonding network suppressed the conformational flexibility of an oligomeric backbone. Cyclization of a rigidified, suitably sized oligomer led to a circular aromatic pentamer. Its crystal structure determined by X-ray crystallography reveals a pseudo five-fold symmetric planarity in the solid state, which is quite unusual among all the previously described shape-persistent macrocycles and synthetic foldamers with biased conformations enforced by noncovalent forces.
• Folding-Promoted TBACl-Mediated Chemo- and Regioselective Demethylations of Methoxybenzene-Based Macrocyclic Pentamers
  作者：Bo Qin、Liuyin Jiang、Sheng Shen、Chang Sun、Weixing Yuan、Sam F. Y. Li、Huaqiang Zeng

  DOI：10.1021/ol202658p

  日期：2011.12.2

  Tetrabutylammonium chloride (TBACI) salt alone has not been shown previously to be capable of removing methoxy groups. It is demonstrated here that the use of TBACI achieves efficient folding-promoted chemo- and regioselective demethylations, eliminating up to two out of five methyl groups situated in similar macrocyclic chemical microenvironments.