5,11,17,23-tetraamino-25,26,27,28-tetramethoxycalix[4]arene | 121935-19-1

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 5,11,17,23-tetraamino-25,26,27,28-tetramethoxycalix[4]arene
• 英文别名: 25,26,27,28-tetramethoxypentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene-5,11,17,23-tetramine
• CAS: 121935-19-1
• 化学式: C₃₂H₃₆N₄O₄
• 分子量: 540.662
• InChiKey: KVWRSUQXPBLQEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  40
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  141
• 氢给体数：
  4
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  硫光气 、 5,11,17,23-tetraamino-25,26,27,28-tetramethoxycalix[4]arene 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以23%的产率得到5,11,17,23-tetraisothiocyanate-25,26,27,28-tetramethoxycalix[4]arene
  参考文献：
  名称：

  探索基于杯芳烃的簇，以有效功能呈现肺炎链球菌糖。

  摘要：

  杯芳烃是有希望的支架，用于多种糖抗原单位的有效簇状暴露。在这里，我们报告合成和生物学评估的六杯肺炎链球菌（SP）血清型19F的三糖重复单元功能的杯[6]芳烃。尽管暴露的糖抗原的数量很少，该系统已显示出其有效抑制天然19F荚膜多糖和抗19F抗体之间结合的能力，很好地模仿了多糖中的抗原决定簇。在初步筛选了四种用N官能化的模型糖杯芳烃之后，已选择使用SP 19F重复单元对calix [6] arene移动支架进行功能化-乙酰甘露糖胺，以及化合价和/或构象性质不同。这项工作是朝着开发新的完全合成的杯芳烃迈出的一步，该杯芳烃包含小的碳水化合物抗原作为潜在的基于碳水化合物的疫苗支架。

  DOI：

  10.1016/j.bioorg.2019.103305
• 作为产物：
  描述：

  5,11,17,23-tetranitro-25,26,27,28-tetramethoxy-calix<4>arene 在 tin(ll) chloride 作用下， 以 乙醇 为溶剂， 生成 5,11,17,23-tetraamino-25,26,27,28-tetramethoxycalix[4]arene
  参考文献：
  名称：

  重新审视四甲氧基杯[4]芳烃：通过自组装进行构象控制

  摘要：

  分子组装中预组织的概念已经确立，它对合成超分子化学的影响是深远的。1 许多自然系统依靠固有的柔性分子的自组织能力而蓬勃发展。这个过程由明确定义的周围结构促进，并在自组装中达到顶峰。2 蛋白质从线性氨基酸序列中找到其热力学最稳定的三级结构的能力就是一个例子。还相关的是两条柔性、互补的多核苷酸链形成双螺旋的能力。在本文中，我们展示了柔性分子如何可逆地自组装以提供明确定义的受体腔。杯 [4] 芳烃骨架 3 被选为对此类现象进行建模的工具。杯芳烃平台最近已被多个实验室用于组装。4,5 我们小组的研究探索了杯 [4] 芳烃框架的独特二聚体结合模式，用于封装小分子客体。 5,6 具体来说，置于杯 [4] 芳烃上缘的尿素功能允许通过头对尾氢键模式发生二聚化（图 1）。众所周知，杯 [4] 芳烃在溶液中的四种离散构象之间相互转化。 3,7 这种构象灵活性可以通过具有大于乙基的取代基的酚氧烷基化来控制，即母体苯酚与

  DOI：

  10.1021/ja962655z

文献信息

• Calix[4]arene-Based Bis[2]catenanes: Synthesis and Chiral Resolution
  作者：Olena Molokanova、Anca Bogdan、Myroslav O. Vysotsky、Michael Bolte、Tomoyuki Ikai、Yoshio Okamoto、Volker Böhmer

  DOI：10.1002/chem.200601814

  日期：2007.7.16

  dimers between tetraaryl and tetratosylurea calix[4]arenes has been used to prepare a series of ten "bisloop" tetraurea calix[4]arenes 3, in which adjacent phenylurea groups are covalently linked through alpha,omega-dioxyalkane chains. This dimerization with tetratosylurea 2 as template preorganizes the alkenyl residues of tetra(m-alkenyloxyphenyl) ureas 1 and enables their selective connection in

  四芳基和四甲苯脲杯[4]芳烃之间氢键键合二聚体的排他形成已用于制备一系列十个“双环”四脲杯[4]芳烃3，其中相邻的苯基脲基团通过α，ω-共价连接。二氧烷链。以四甲苯磺酰脲2为模板的这种二聚作用使四（间-烯基氧基苯基）脲1的烯基残基预先组织化，并通过烯烃复分解然后氢化使它们以高产率（高达95％）选择性连接。“双环”杯芳烃3也仅与1形成异二聚体。因此，在一个单独的复分解/氢化序列中，一系列14个环状双[2]邻苯二酚4，其中两个杯[4]芳烃通过它们的宽边连接在一起。两对互锁的环（总大小为29到41个原子），制备的收率高达97％。通过手性固定相的HPLC研究了这些手性双[2]邻苯二甲酰胺的光学拆分。一个实施例（4（P，10））的单晶X射线结构证实了互锁环，并表明可以“完全”打开杯[4]芳烃的氢键二聚体胶囊。
• Synthesis of huge macrocycles using two calix[4]arenes as templates
  作者：Yudong Cao、Leyong Wang、Michael Bolte、Myroslav O. Vysotsky、Volker Böhmer

  DOI：10.1039/b505223h

  日期：——

  Macrocycles with up to 100 atoms have been synthesised using two calix[4]arenes as templates: first, (3,5-dialkenyloxy)phenyl groups are attached to the wide rim of a calix[4]arene via urea links, then the alkenyl groups are connected via a metathesis reaction using a tetratosylurea calix[4]arene for their correct prearrangement and finally the urea functions are cleaved to detach the newly formed

  使用两个杯[4]芳烃作为模板合成了最多具有100个原子的大环：首先，（3,5-二烯基氧基）苯基通过脲键连接到杯[4]芳烃的宽边上，然后烯基使用四甲苯脲杯[4]芳烃通过易位反应连接两个基团，以进行正确的预先安排，最后将尿素官能团裂解以分离新形成的大环。
• Guest exchange in dimeric capsules formed by tetra-urea calix[4]arenes
  作者：Ivan Vatsouro、Ellen Alt、Myroslav Vysotsky、Volker Böhmer

  DOI：10.1039/b719053k

  日期：——

  Ten tetra-urea calix[4]arene derivatives with different ether residues (methyl, pentyl, benzyl, all combinations of methyl and pentyl, 1,3-dibenzyl-2,4-dipentyl), including also the tetrahydroxy compound and the 1,3-dipentyl ether, were synthesised. Their urea groups were substituted with a lipophilic residue to ensure sufficient solubility in cyclohexane. Thus, kinetics for the exchange of the included guest (benzene) against the solvent (cyclohexane) could be followed by 1H NMR spectroscopy. The apparent first order rate constants decrease with increasing size of the ether residues from methyl to benzyl by more than three orders of magnitude. This can be understood by a decreasing flexibility/mobility of the calixarene skeleton. In line with this explanation is the rather slow exchange for the tetrahydroxy compound, where the cone conformation is stabilised by a cyclic array of intramolecular OH⋯OH hydrogen bonds.

  我们合成了十种具有不同醚残基（甲基、戊基、苄基、甲基和戊基的所有组合、1,3-二苄基-2,4-二戊基）的四脲钙[4]炔衍生物，其中还包括四羟基化合物和 1,3- 二戊基醚。它们的脲基被亲脂残基取代，以确保在环己烷中有足够的溶解度。因此，可以通过 1H NMR 光谱跟踪所含客体（苯）与溶剂（环己烷）的交换动力学。随着醚残基（从甲基到苄基）大小的增加，表观一阶速率常数降低了三个数量级以上。这可以用卡利卡林骨架的柔韧性/流动性降低来解释。与这一解释相一致的是四羟基化合物的交换相当缓慢，锥形构象通过分子内 OH⋯OH 氢键的循环阵列而稳定。
• Glucosylthioureidocalix[4]arenes: Synthesis, conformations and gas phase recognition of amino acids
  作者：Mika Torvinen、Raisa Neitola、Francesco Sansone、Laura Baldini、Rocco Ungaro、Alessandro Casnati、Pirjo Vainiotalo、Elina Kalenius

  DOI：10.1039/b916268b

  日期：——

  The gas-phase recognition of native amino acids and the conformational properties of three glucosylthioureidocalix[4]arenes (1-3) were studied theoretically and experimentally using ab initio calculations, ESI-FTICR,1H and 13C NMR MS. The conformational and complexation properties of the glucocalixarenes were dependent on the number of glucose units at the upper rim and the length of the alkyl chains at the lower rim of the calixarene skeleton. ESI-MS experiments showed the compounds to form 1 : 1 complexes with the amino acids, with a marked preference for amino acids containing an aromatic nucleus and an additional H-bonding group in their side chain (Trp, Tyr, Phe ≫ Ser, Leu and Asp). The experimental data were rationalized by the results of ab initio calculations. ESI-MS competitions carried out with enantiomeric-labelled (EL) amino acids showed enantiomeric selectivities ranging from 0.61 (Phe(D)/Phe(L) with ligand 3) to 2.58 (Tyr(D)/Tyr(L) with ligand 2). In gas-phase hydrogen–deuterium (H/D) exchange reactions, diglucosylcalix[4]arene 2 exhibited extremely slow exchange rates, which were attributed to the close proximity and strong hydrogen bonding between the facing glucosylthioureido groups. H/D exchange rates were much higher for the tetraglucosylcalix[4]arenes 1 and 3 and their amino acid complexes, and the more rigid tetrapropoxy derivative 3 showed more selective H/D exchange reactions than the calixarene 1. Bi- or trimodal H/D exchange distribution was observed for the tetraglucosyl derivatives indicating that these ligands exist in multiple isomeric forms in gas phase.

  研究人员利用 ab initio 计算、ESI-FTICR、1H 和 13C NMR MS 对三种葡萄糖硫代二碳六[4]烯（1-3）的气相识别原生氨基酸和构象特性进行了理论和实验研究。糖基卡利克沙烯烃的构象和复合特性取决于卡利克沙烯烃骨架上缘葡萄糖单元的数量和下缘烷基链的长度。ESI-MS 实验表明，这些化合物与氨基酸形成 1 ：氨基酸形成 1 : 1 的络合物，其中含有芳香核并在其侧链中含有额外 H 键基团的氨基酸（Trp、Tyr、Phe ≫ Ser、Leu 和 Asp）具有明显的偏好性。实验数据通过 ab initio 计算结果得到了合理的解释。用对映体标记（EL）的氨基酸进行的 ESI-MS 比对显示，对映体选择性从 0.61（Phe(D)/Phe(L)，配体 3）到 2.58（Tyr(D)/Tyr(L)，配体 2）不等。在气相氢-氘（H/D）交换反应中，二葡糖基钙钛矿[4]炔 2 的交换速率极慢，这是因为面对面的葡糖基硫脲基团之间的距离很近，而且氢键很强。四葡糖基萼[4]炔 1 和 3 及其氨基酸复合物的 H/D 交换速率要高得多，而且刚性更强的四丙氧基衍生物 3 比萼[4]炔 1 表现出更高的选择性 H/D 交换反应。在四葡糖基衍生物中观察到了双峰或三峰 H/D 交换分布，表明这些配体在气相中以多种异构体形式存在。
• Solvent-Induced Amphiphilic Molecular Baskets:  Unimolecular Reversed Micelles with Different Size, Shape, and Flexibility
  作者：Eui-Hyun Ryu、Jie Yan、Zhenqi Zhong、Yan Zhao

  DOI：10.1021/jo0607663

  日期：2006.9.1

  Amphiphilic molecular baskets were obtained by attaching facially amphiphilic cholate groups to a covalent scaffold (calix[4] arene or 1,3,5-2,4,6-hexasubstituted benzene). In a solvent mixture consisting of mostly a nonpolar solvent (i.e., CCl4) and a polar solvent (i.e., DMSO), the hydrophilic faces of cholates turned inward to form a reversed-micelle-like conformer whose stability was strongly influenced by the number of the cholates and the topology of the scaffold. Preferential solvation of the hydrophilic faces of cholates within the molecule by the polar solvent was cooperative and gave the fundamental driving force to the conformational change. The reversed-micelle-like conformer was most stable in structures that allowed multiple cholates to form a microenvironment that could efficiently enrich the polar solvent molecules from the bulk solvent mixture.