5-Formyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene | 137014-56-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5-Formyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene
• 英文别名: formyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene；5-Formyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene；25,26,27,28-Tetrakis(2-ethoxyethoxy)pentacyclo[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-carbaldehyde
• CAS: 137014-56-3
• 化学式: C₄₅H₅₆O₉
• 分子量: 740.934
• InChiKey: NSPSPDCNYDUTDH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  54
• 可旋转键数：
  21
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  90.9
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  5-Formyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene 在 palladium on activated charcoal 氢气 、 三乙胺 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 36.0h， 生成 5-<(N-Boc-N-methyl)aminomethyl>-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene
  参考文献：
  名称：

  Dinuclear and Trinuclear Zn(II) Calix[4]arene Complexes as Models for Hydrolytic Metallo-Enzymes. Synthesis and Catalytic Activity in Phosphate Diester Transesterification

  摘要：

  Calix[4]arenes modified with two or three Zn(II)-2,6-bis(aminomethyl)pyridyl groups,. 3-[Zn](2) and (3)[Zn](3), respectively, were investigated as models for dinuclear and trinuclear metallo-enzymes that catalyze the cleavage of phosphate diesters. Under neutral conditions, 0.48 mM of 3-[Zn](2) causes a rate acceleration of 23 000 in the transesterification of the RNA model substrate 2-hydroxyproyl-p-nitrophenyl phosphate (HPNP, 0.19 mM). Comparison with the activities of a mononuclear complex 2-[Zn] and a reference complex lacking the calix[4]arene backbone 1-[Zn] shows that the catalysis is due to cooperative action of the Zn(II) centers and indicates that hydrophobic effects contribute to the catalysis. Saturation kinetics and pH variation studies demonstrate that the high catalytic activity of the flexible complex 3-[Zn](2) originates from a very high substrate binding affinity, affording a Michaelis-Menten complex in which the substrate is converted with a relatively moderate rate. A rigid analogue 4-[Zn](2) exhibits both a lower substrate binding strength and a lower catalytic rate. This demonstrates the importance of a certain flexibility between the cooperating catalytic centers. The trinuclear complex 5-[Zn](3) induces a rate acceleration of 32 000 times, and shows a decreased substrate binding and an increased catalytic rate compared to its dinuclear analogue 3-[Zn](2). In a possible mechanism two Zn(II) ions activate the phosphoryl group and another activates the beta-hydroxyl group of HPNP.

  DOI：

  10.1021/jo982201f
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 在 三氯化铝 、 四氯化锡 、 sodium hydride 、 苯酚 作用下， 以 氯仿 、 甲苯 为溶剂， 反应 0.5h， 生成 5-Formyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene
  参考文献：
  名称：

  Synthesis of selectively formylated calixarene ethers

  摘要：

  By careful choice of a catalyst (TiCl4 or SnCl4) temperature, reaction time and mole ratio of the substrate to dichloromethyl-methylether, it has been possible to obtain new functionalized formylated calix[n]arenes in the cone or partial cone conformation. Optimized general reaction procedures for obtaining mono-, di-, tri- and tetraformylated derivatives of calix[4]arenes as exemplified by formylation of tetramethoxy-, tetrakis(2-ethoxyethoxy)-, bis(ethoxycarbonylmethoxy)- and bis(hexadecyloxy)-calix[4]-arenes have been reported. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(02)00551-3

文献信息

• Synthesis of Dithiane-Based Photolabile Molecular Systems
  作者：Andrei Kutateladze、Oleg Mitkin、Yongqin Wan、Alexei Kurchan

  DOI：10.1055/s-2001-15057

  日期：——

  Synthesis 2001, No. 8, 18 06 2001. Article Identifier: 1437-210X,E;2001,0,08,1133,1142,ftx,en;C00801SS.pdf. © Georg Thieme Verlag Stuttgart · New York ISSN 0039-7881 Abstract: Synthesis of photolabile molecular systems based on lithiodithiane addition to carbonyl compounds is described. Dithianes of the spiro structure, e.g., 2,4,8,10-tetrathiaspiro[5.5]undecane and 2,4-dithia-8,10-dioxaspiro[5.5]undecane

  Synthesis 2001, No. 8, 18 06 2001. 文章标识符：1437-210X,E;2001,0,08,1133,1142,ftx,en;C00801SS.pdf。© Georg Thieme Verlag Stuttgart · 纽约 ISSN 0039-7881 摘要：描述了基于二硫代锂加成羰基化合物的光不稳定分子系统的合成。螺结构的二噻烷，例如 2,4,8,10-四噻螺[5.5]十一烷和 2,4-二噻-8,10-二氧杂螺[5.5]十一烷被用作系链，因此允许采用模块化方法来构建一组不同的光裂解分子。发现从简单取代的苯甲醛到甲酰化苯并冠醚、碳水化合物或杯芳烃的各种羰基化合物都适用于这种化学。
• Selective formylation of calix[4]arenes at the ‘upper rim’ and synthesis of new cavitands
  作者：Arturo Arduini、Giuseppe Manfredi、Andrea Pochini、Anna Rita Sicuri、Rocco Ungaro

  DOI：10.1039/c39910000936

  日期：——

  The direct selective upper rim 1,3-formylation of conformationally rigid calyx[4]arenes is achieved for the first time; the diametrical bis(formyl)calix[4]arene 4 is used as a key intermediate for the synthesis of new cavitands.

  首次实现构象刚性花萼[4]芳烃的直接选择性上边缘1,3-甲酰化；径向双（甲酰基）杯[4]芳烃4被用作合成新空泡分子的关键中间体。
• Differential and Substrate-Selective Reactivity of Calix[4]arene Derivatives with Cyclenyl-Zn(II) Modifications at the Upper Rim
  作者：Gulsum Ozturk、Engin U. Akkaya

  DOI：10.1021/ol0360694

  日期：2004.1.1

  see text] Novel "cone conformation" calix[4]arene derivatives, carrying either one or two cyclen (1,4,7,10-tetra-azacyclododecane) moieties at the upper rim, have been synthesized. The hydrolytic activities of the Zn(II) complexes of these calixarenes were studied. A surprising behavior was observed with p-nitrophenylstearate; whereas the bis-cyclenyl-2Zn(II) complex showed negligible hydrolytic activity

  合成了新颖的“圆锥构象”杯[4]芳烃衍生物，其在上边缘带有一个或两个环（1,4,7,10-四氮杂环十二烷）部分。研究了这些杯芳烃的Zn（II）配合物的水解活性。用对-硝基苯基硬脂酸酯观察到令人惊讶的行为。而双环烯基-2Zn（II）配合物在背景下的水解活性可忽略不计，而单核配合物在pH 8.5时显示出明显的400倍速率增加。
• Transition metal-directed self-assembly of calix[4]arene based dithiocarbamate ligands
  作者：Philip R. A. Webber、Michael G. B. Drew、Richard Hibbert、Paul D. Beer

  DOI：10.1039/b400929k

  日期：——

  metal-directed self-assembly of dithiocarbamate ligand functionalized upper and lower rim calix[4]arenes affords novel dimeric bimetallic bis(calix[4]arene) species as determined by a combination of analytical methods including X-ray crystallography. An exception is a zinc(II) dithiocarbamate upper rim calix[4]arene assembly which is monomeric in nature. Electrochemical investigations reveal the bimetallic copper(II)

  二硫代氨基甲酸酯配体官能化的上边缘和下边缘杯[4]芳烃的过渡金属定向自组装提供了新颖的二聚双金属双（杯[4]芳烃）物种，通过结合包括X射线晶体学在内的分析方法测定。一个例外是二硫代氨基甲酸锌（II）上边缘杯[4]芳烃组件，其性质为单体。电化学研究表明，双金属铜（II）双（杯[4]芳烃）系统可通过各自的铜（II）/（III）二硫代氨基甲酸酯氧化波的显着阴极扰动来电化学检测磷酸二氢盐和羧酸根阴离子。
• Highly efficient intramolecular Cannizzaro reaction between 1,3-distal formyl groups at the upper rim of a cone-calix[4]arene
  作者：Marzia Galli、José Augusto Berrocal、Stefano Di Stefano、Roberta Cacciapaglia、Luigi Mandolini、Laura Baldini、Alessandro Casnati、Franco Ugozzoli

  DOI：10.1039/c2ob25458a

  日期：——

  The 1,3-distal cone-calix[4]arene dialdehyde 1 undergoes Cannizzaro disproportionation in the presence of strong base, but its 1,2-vicinal regioisomer 3 and the analogous monoaldehyde 2 are unreactive under the same conditions. The high intramolecular reactivity of the 1,3-distal regioisomer 1 is measured and discussed in terms of Effective Molarity (EM).

  在强碱存在下，1,3-二叉锥-萼[4]炔二甲醛 1 会发生坎尼扎罗歧化反应，但在相同条件下，它的 1,2- 单向生殖异构体 3 和类似的单醛 2 却不发生反应。我们用有效摩尔度（EM）测量并讨论了 1,3-二取代基异构体 1 的高分子内反应性。