5,17-diamino-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]-arene | 144080-18-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,17-diamino-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]-arene
• 英文别名: 1,3-diaminocalix[4]arene
• CAS: 144080-18-2
• 化学式: C₄₄H₅₈N₂O₈
• 分子量: 742.953
• InChiKey: BGDGVGJABFRTSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.19
• 重原子数：
  54.0
• 可旋转键数：
  20.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  125.88
• 氢给体数：
  2.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  5,17-diamino-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]-arene 在 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 5,17-bis-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene
  参考文献：
  名称：

  上缘桥杯[4]芳烃气相中性分子的络合

  摘要：

  已经合成了在上边缘的直径桥接的杯[4]芳烃，其分子单元带有二甲苯基或2，4-己二炔基。桥的形状，刚度和化学结构决定了这些体系对气相中性分子的主客体络合特性。

  DOI：

  10.1016/0040-4020(94)00919-l
• 作为产物：
  描述：

  25,26,27,28-Tetrakis(2-ethoxyethoxy)-5,17-dinitrocalix<4>arene 在 palladium on activated charcoal 、 一水合肼 作用下， 以 乙醇 为溶剂， 以74%的产率得到5,17-diamino-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]-arene
  参考文献：
  名称：

  Upper Rim Guanidinocalix[4]arenes as Artificial Phosphodiesterases

  摘要：

  Calix[4]arene derivatives, blocked in the cone conformation and functionalized with two to four guanidinium units at the upper rim were synthesized and investigated as catalysts in the cleavage of the RNA model compound 2-hydroxypropyl p-nitrophenyl phosphate. When compared with the behavior of a monofunctional model compound, the catalytic superiority of the calix[4]arene derivatives points to a high level of cooperation between catalytic groups. Combination of acidity measurements with the pH dependence of catalytic rates unequivocally shows that a necessary requisite for effective catalysis is the simultaneous presence, on the same molecular framework, of a neutral guanidine acting as a general base and a protonated guanidine acting as an electrophilic activator. The additional guanidinium (guanidine) group in the diprotonated (monoprotonated) trifunctional calix[4]arene acts as a more or less innocent spectator. This is not the case with the tetrasubstituted calix[4]arene, whose mono-, di-, and triprotonated forms are slightly less effective than the corresponding di- and triguanidinocalix[4]arene derivatives, most likely on account of a steric interference with HPNP caused by overcrowding.

  DOI：

  10.1021/jo300193y
• 作为试剂：
  描述：

  (S)-(+)-2-cyano-2-methylphenylacetic acid 在 5,17-diamino-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]-arene 作用下， 以 二氯甲烷-D2 为溶剂， 反应 4.17h， 生成 α-甲基苯腈
  参考文献：
  名称：

  利用化学燃料对杯[4]芳烃支架进行时间可编程的锁定/解锁。

  摘要：

  在这项工作中，我们报道了2-氰基-2-苯基丙酸和其p -Cl，p -CH 3和p -OCH 3衍生物可用作化学燃料，以控制其圆锥构象的杯[4]芳烃骨架的几何形状。结果表明，在燃料的作用下，圆锥杯[4]芳烃平台呈“锁定”形状，两个相对的芳环强烈会聚，另外两个强烈发散（“夹锥”构象）。仅当燃料耗尽时，圆锥杯[4]芳烃支架才会恢复其静止的“解锁”形状。值得注意的是，“锁定”状态的持续时间可以通过改变燃料结构或数量随意控制。该过程的动力学研究表明，燃料的消耗是由“解锁的”杯芳烃催化的，该杯芳烃充当其自身生产的自催化剂。提出了一种用于燃料消耗反应的机制。

  DOI：

  10.1002/chem.202002574

文献信息

• Synthesis of potential receptor molecules by combination of upper-rim-functionalized calix[4]arenes and partly bridged resorcinarenes
  作者：Peter Timmerman、Harold Boerrigter、Willem Verboom、David N. Reinhoudt

  DOI：10.1002/recl.19951140306

  日期：——

  Combination of upper-rim-1,3-difunctionalized calix[4]arenes 14, 16, and 18 with tribridged resorcinarenes 4 and 6 and A,C-di-bridged resorcinarenes 10 and 13 yields both 1/1 calix-resorcinarenes (22–24) and 2/1 calix-resorcinarenes (25, 26). 1/1 Calix-resorcinarene 22 mainly exists as one conformer (a), but at low temperatures (−60°C) very small amounts ( < 5%) of a second conformer (b) can be observed

  上边缘1,3-双官能度杯[4]芳烃14、16和18与三桥间苯二烃4和6以及A，C-二桥间苯二酚10和13的结合产生1/1杯-间苯二烃（22 –24）和2/1杯-间苯二酚（25，26）。1/1杯型间苯二芳烃22主要作为一种构象异构体（a）存在，但是在低温（-60℃ ）下，可以观察到非常少量（＜5％）的第二种构象异构体（b）。两种构象异构体均通过绕一个C（芳烃）-N键旋转而达到平衡，并具有活化自由能（ΔG ≠）为13 kcal / mol。2/1 Calix-间苯二酚25和26更具柔韧性，并且以构象异构体的混合物形式存在。为了能够通过杯[4]芳烃片段之间的刚性间隔基来刚性化2/1杯-间芳烃芳烃的结构，合成了带有硝基，羧基的1,3-二氨基杯[4]芳烃衍生物31、32和34酯和未取代的芳环上的氰基。利用这些杯[4]芳烃衍生物，合成了三个新的功能化的2/1杯-间苯二碳烯芳烃35-37。
• Synthesis of New Chiral Ligands by Capping of Calix[4]arene Derivatives
  作者：Evgueni Pinkhassik、Ivan Stibor、Vladimír Havlíček

  DOI：10.1135/cccc19961182

  日期：——

  Calix[4]arene derivatives are used as a scaffold for the attachment of chiral substituents. Calix[4]arenes having either lower or upper rim capped with chiral binaphtholic species 5 and 6, as well as new biscalix[4]arenodiaza-18-crown-6 (8), have been synthesized.

  Calix[4]芳烃衍生物被用作连接手性取代基的支架。已合成具有手性双萘基物种5和6的下缘或上缘被封顶的Calix[4]芳烃，以及新的双Calix[4]芳烃二氮杂18-冠-6（8）。
• NMR Complexation Study of Several Oxyethylated Calix[4]arenes with Lithium, Sodium and Potassium Ions
  作者：Jaroslav Havlíček、Marcela Tkadlecová、Michaela Vyhnánková、Evgueni Pinkhassik、Ivan Stibor

  DOI：10.1135/cccc19961783

  日期：——

  The influence of calix[4]arene upper rim substitution on the complexation with Li⁺, Na⁺, K⁺ was studied by ¹H NMR spectroscopy. Calix[4]arenes 1-4 namely 25,26,27,28-tetrakis(3-oxapentyloxy)calix[4]arene (1), its 5,17-diamino (2) and 5,17-dinitro derivative (3) as well as 25,26,27,28-tetrakis(3,6,9-trioxadecyloxy)calix[4]arene (4) having four monoalkyloligoethylene glycol chains on the lower rim have been studied. No complexation has been observed for Li⁺. Two electron-donating NH₂ groups on the calixarene upper rim (compound 2) improve the complexation ability for Na⁺ and K⁺ compared with parent calixarene 1. The electron-withdrawing nitro groups in 3 have the opposite influence. It seems that the complexation of alkali metal ions studied is not significantly influenced by the increasing number of donor atoms (from eight in 1 to sixteen in 4) available for complexation on the lower rim. The position of sodium cation in 1 . Na⁺ and 4. Na⁺ is supposed to be in close proximity of phenolic oxygens based on ¹H and ¹³C NMR data. The error analysis is given for the stability constant determination from NMR data.

  使用1H NMR光谱研究了Calix [4]芳烃上缘取代对其与Li +，Na +，K +络合作用的影响。研究了四个单烷基寡乙二醇链被连接到下缘的Calix [4]芳烃1-4，即25,26,27,28-四(3-氧代戊氧基)Calix [4]芳烃（1），其5,17-二氨基（2）和5,17-二硝基衍生物（3）以及25,26,27,28-四(3,6,9-三氧代癸氧基)Calix [4]芳烃（4）。没有观察到Li +的络合。Calix芳烃上缘的两个电子给予的NH2基团（化合物2）与父Calix芳烃1相比，提高了Na +和K +的络合能力。电子吸引的硝基团在3中具有相反的影响。研究的碱金属离子的络合似乎不受可用于下缘络合的给体原子数量（从1中的8到4中的16）的增加的显著影响。根据1H和13C NMR数据，Na +在1.Na +和4.Na +的位置应该靠近酚氧基。给出了从NMR数据确定稳定常数的误差分析。
• Hydrogen bonded calix[4]arene aggregates
  作者：Jan-Dirk van Loon、Rob G. Janssen、Willem Verboom、David N. Reinhoudt

  DOI：10.1016/s0040-4039(00)61208-x

  日期：1992.8

  Calix[4]arenes in a rigid cone conformation that contain selfcomplementary alpha-pyridone moieties at the upper rim, form aggregates in CDCl3 solution, which can be denaturated by the formation of a complex with urea derivatives.