N,N',N'',N''',N'''',N'''''-hexamethylazacalix[6](2,6)pyridine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: N,N',N'',N''',N'''',N'''''-hexamethylazacalix[6](2,6)pyridine
• 英文别名: methylazacalix[6]pyridine；azacalix[6]pyridine；Py6；2,8,14,20,26,32-Hexamethyl-2,8,14,20,26,32,37,38,39,40,41,42-dodecazaheptacyclo[31.3.1.13,7.19,13.115,19.121,25.127,31]dotetraconta-1(37),3(42),4,6,9(41),10,12,15(40),16,18,21,23,25(39),27,29,31(38),33,35-octadecaene
• 化学式: C₃₆H₃₆N₁₂
• 分子量: 636.762
• InChiKey: GWJKJXZMDDWZCP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  48
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  107
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  silver trifluoromethanesulfonate 、 N,N',N'',N''',N'''',N'''''-hexamethylazacalix[6](2,6)pyridine 在 [1,3,5-(CCAg)₃-C₆H₃]_n 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.17h， 以66%的产率得到
  参考文献：
  名称：

  Designed synthesis of a metal cluster-pillared coordination cage

  摘要：

  通过一种大循环定向策略，构建了一种前所未有的多核金属簇柱三角棱镜。通过单晶 X 射线晶体学和光谱学研究，对三种银簇参与的金属超分子的离散结构进行了表征。

  DOI：

  10.1039/c2cc36250c
• 作为产物：
  描述：

  6-溴-2-甲基氨基吡啶 在 tris-(dibenzylideneacetone)dipalladium(0) 三叔丁基膦 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 以8%的产率得到N,N',N'',N''',N'''',N'''''-hexamethylazacalix[6](2,6)pyridine
  参考文献：
  名称：

  Preparation of new type of azacalixarene, azacalix[n](2,6)pyridine

  摘要：

  Palladium-catalyzed aryl amination of 2,6-dibromopyridine with 2,6-bis(methylamino)pyridine or 2-bromo-6-(methylamino)pyridine gave new azacalix[n](2,6)pyridines (n=4 and 6). Molecular structure, conformation, and complexation of the macrocycles toward zinc ion were characterized by NMR spectroscopy and X-ray crystallography. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)01842-7

文献信息

• Designed synthesis of size-tunable Ag₂S nanoclusters via distinguishable C–S bond cleavage reaction of alkyl- and aryl-thiolates
  作者：Hang-Qing Chen、Xin He、Hui Guo、Nan-Yan Fu、Liang Zhao

  DOI：10.1039/c4dt04021j

  日期：——

  We report herein the synthesis of two different silver clusters of aryl- and alkyl-thiolates. These two cluster complexes exhibited biased C–S bond cleavage reaction rates upon removing protective hexamethylazacalix[6]pyridine (Py[6]) ligands, which was applied in the fabrication of silver sulfide nanoclusters with variable and controllable sizes.

  我们在此报告了芳基-和烷基-硫醇盐的两个不同银簇的合成。去除保护性六甲基氮杂aca [6]吡啶（Py [6]）配体后，这两个簇复合物显示出偏向的C–S键裂解反应速率，该配体被用于制备大小可变且可控制的硫化银纳米簇。
• Synthesis, Structure, and Fullerene-Complexing Property of Azacalix[6]aromatics
  作者：Shi-Xin Fa、Li-Xia Wang、De-Xian Wang、Liang Zhao、Mei-Xiang Wang

  DOI：10.1021/jo5003714

  日期：2014.4.18

  Synthesis, structure, and fullerene-binding property of azacalix[6]aromatics were systematically studied. By means of [3 + 3] and [2 + 2 + 2] fragment coupling protocols, a number of azacalix[6]aromatics containing different combinations of benzene, pyridine, and pyrimidine rings and various substituents on the bridging nitrogen atoms were synthesized conveniently in moderate to good yields. The resulting

  系统研究了氮杂杯[6]芳烃的合成，结构和富勒烯结合性能。通过[3 + 3]和[2 + 2 + 2]片段偶联方案，可以方便地合成许多含有苯，吡啶和嘧啶环的不同组合以及桥接氮原子上各种取代基的氮杂杯[6]芳族化合物中等至良好的产量。生成的大环化合物根据芳香族结构单元采用固态对称且畸变严重的1,3,5-交替构象，而在溶液中，它们以相对于NMR时间尺度快速互换的构象异构体的混合物形式存在。所有大环化合物都能与C 60和C 70形成1：1的配合物在甲苯中的缔合常数最高为7.28×10 4 M –1。在结晶状态下，氮杂杯[6]芳烃与C 60和C 70形成配合物，客体和客体之间的化学计量比为2：1、1：1和1：2。Azacalix [6]芳烃主要通过形成夹心结构与富勒烯相互作用，其中C 60或C 70被两个大环夹在中间。X射线分子结构显示，凹的azacalix [6]芳烃与凸的富勒烯C 60和C 70之
• Macrocyclic-ligand Induced Synthesis of Aryl Ethynides with Divergent Silver(I) Clusters
  作者：Guangmian Ji、Siqi Zhang、Sam C. K. Hau、Liang Zhao

  DOI：10.1002/cjoc.201700481

  日期：2017.12

  5‐(C ≡ C)4C6H2)(Py[6])2(CF3SO3)8]·4MeOH·3H2O (2) are synthesized through the interaction with a bowl‐shaped macrocyclic ligand Py[6]. Particularly, two dissimilar silver(I) clusters are resulted in 2 within the structure under the influence of the macrocyclic ligand Py[6]. Such dissimilarity of the silver(I) cluster is also reflected on the structural and photophysical differences between 1 and 2.

  两种具有结构特征的以金属簇为中心的超分子体系结构，名为[Ag 8（1,2-（CC C）2 -C 6 H 4）（Py [6]）（CF 3 CO 2）6 ]·2.5MeOH（1）和[Ag 12（1,2,4,5-（C≡C）4 C 6 H 2）（Py [6]）2（CF 3 SO 3）8 ]·4MeOH·3H 2 O（2）为通过与碗形大环配体Py [6]相互作用而合成。尤其是，在大环配体Py [6]的影响下，结构中有2个不同的银（I）簇。银（I）团簇的这种不同也反映在1和2之间的结构和光物理差异上。
• Synthesis of Large Macrocyclic Azacalix[<i>n</i>]pyridines (<i>n</i> = 6 − 9) and Their Complexation with Fullerenes C₆₀ and C₇₀
  作者：En-Xuan Zhang、De-Xian Wang、Qi-Yu Zheng、Mei-Xiang Wang

  DOI：10.1021/ol800840m

  日期：2008.6.1

  Large methylazacalix[n]pyridines (n = 6-9) were synthesized effectively from the Pd-catalyzed macrocyclic fragment coupling reactions between alpha,omega-dibrominated and alpha,omega-diaminated linear oligomers. As macrocyclic host molecules, they formed a 1:1 complex with fullerenes C-60 and C-70 with association constants ranging from 3 x 10(4) to 1 x 10(5) M-1.
• Stabilization of a Reactive Polynuclear Silver Carbide Cluster through the Encapsulation within a Supramolecular Cage
  作者：Cai-Yan Gao、Liang Zhao、Mei-Xiang Wang

  DOI：10.1021/ja209729h

  日期：2012.1.18

  We report herein the synthesis of a new metal cluster-encapsulated supramolecular capsule, [(C C)@Ag5-6@(Py6)(2)](CF3SO3)(3-4)(3, Py6 = azacalix[6]-pyridine), by use of a bowl-shaped macrocyclic ligand Py6. The multinuclear silver carbide cluster aggregate in 3 is encapsulated by two Py6 ligands through both metal-ligand coordination and cation-pi interactions, spotlighting a new synthetic strategy for supramolecular capsules.