5,17-bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene | 166665-14-1

• 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-bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
• 英文别名: 5,17-Bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9(27),10,12,15(26),16,18,21,23-dodecaene
• CAS: 166665-14-1
• 化学式: C₄₆H₅₈Cl₂O₈
• 分子量: 809.868
• InChiKey: GPXYWUOXVCNYRB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  56
• 可旋转键数：
  22
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  73.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5,17-bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.5h， 生成 5,17-Bis(azidomethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9(27),10,12,15(26),16,18,21,23-dodecaene
  参考文献：
  名称：

  Synthesis and metal-binding properties of [60]fullerene-linked calix[4]arenes: an approach to ‘exohedral metallofullerenes’

  摘要：

  首次合成了“富勒烯基冠醚”，其中[60]富勒烯通过两个载体链共价连接到锥形冠醚[4]芳烃1或连接到1,3-交替冠醚[4]芳烃2。虽然金属阳离子加入后2的吸收光谱几乎没有变化，但1的吸收光谱受加入的Li+、Na+和Ag+的影响，表明形成了外接的[60]富勒烯-金属配合物。

  DOI：

  10.1039/a707258i
• 作为产物：
  描述：

  5,17-diformyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix<4>arene 在 吡啶 、 锂硼氢 、 氯化亚砜 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 9.0h， 生成 5,17-bis(chloromethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
  参考文献：
  名称：

  Synthesis and metal-binding properties of [60]fullerene-linked calix[4]arenes: an approach to ‘exohedral metallofullerenes’

  摘要：

  首次合成了“富勒烯基冠醚”，其中[60]富勒烯通过两个载体链共价连接到锥形冠醚[4]芳烃1或连接到1,3-交替冠醚[4]芳烃2。虽然金属阳离子加入后2的吸收光谱几乎没有变化，但1的吸收光谱受加入的Li+、Na+和Ag+的影响，表明形成了外接的[60]富勒烯-金属配合物。

  DOI：

  10.1039/a707258i

文献信息

• Syntheses and characterizations of two copolymers containing cone conformations of calix[4]arenes in the polymer backbone
  作者：Michael T. Blanda、Eba Adou

  DOI：10.1039/a704122e

  日期：——

  Two new polymers containing calix[4]arenes in the cone conformation were synthesized via condensation reactions.

  通过缩合反应合成了两种含有锥形构象钙[4]炔的新型聚合物。
• 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。
• Catalysis of Diribonucleoside Monophosphate Cleavage by Water Soluble Copper(II) Complexes of Calix[4]arene Based Nitrogen Ligands
  作者：Roberta Cacciapaglia、Alessandro Casnati、Luigi Mandolini、David N. Reinhoudt、Riccardo Salvio、Andrea Sartori、Rocco Ungaro

  DOI：10.1021/ja0632106

  日期：2006.9.1

  Calix[4]arenes functionalized at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with [12]ane-N-3 ligating units were synthesized, and their bi-and trimetallic zinc(II) and copper( II) complexes were investigated as catalysts in the cleavage of phosphodiesters as RNA models. The results of comparative kinetic studies using monometallic controls indicate that the subunits of all of the zinc(II) complexes and of the 1,3-distal bimetallic copper(II) complex 7-Cu-2 act as essentially independent monometallic catalysts. The lack of cooperation between metal ions in the above complexes is in marked contrast with the behavior of the 1,2-vicinal bimetallic copper(II) complex 6-Cu-2, which exhibits high catalytic efficiency and high levels of cooperation between metal ions in the cleavage of HPNP and of diribonucleoside monophosphates NpN'. A third ligated metal ion at the upper rim does not enhance the catalytic efficiency, which excludes the simultaneous cooperation in the catalysis of the three metal ions in 8-Cu-3. Rate accelerations relative to the background brought about by 6-Cu-2 and 8-Cu-3 (1.0 mM catalyst, water solution, pH 7.0, 50 degrees C) are on the order of 10(4)-fold, largely independent of the nucleobase structure, with the exception of the cleavage of diribonucleoside monophosphates in which the nucleobase N is uracil, namely UpU and UpG, for which rate enhancements rise to 10(5)-fold. The rationale for the observed selectivity is discussed in terms of deprotonation of the uracil moiety under the reaction conditions and complexation of the resulting anion with one of the copper(II) centers.
• Ribonuclease Activity of an Artificial Catalyst That Combines a Ligated Cu^II Ion and a Guanidinium Group at the Upper Rim of a <i>cone</i>-Calix[4]arene Platform
  作者：Riccardo Salvio、Stefano Volpi、Roberta Cacciapaglia、Alessandro Casnati、Luigi Mandolini、Francesco Sansone

  DOI：10.1021/acs.joc.5b00965

  日期：2015.6.5

  A cone-calix[4]arene derivative, featuring a guanidinium group and a Cu-II ion ligated to a I,4,7-triazacyclononane (TACN) ligand at the 1,3-distal positions of the upper rim, effectively catalyzes the cleavage of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) and a number of diriboimdeoside 3',5'-monophosphates (NpN'). Kinetic and potentiometric measurements support the operation of a general-base/general-acid mechanism and demonstrate that the hydroxo form of the ligated Cu-II ion is the sole catalytically active species. Rate enhancements relative to the background hydrolysis reaction at 1 mM catalyst concentration are 6 x 10(5)-fold for HPNP and cluster around 10(7)-fold with the most favorable catalyst-NpN' combinations.
• Direct Regioselective Formylation of Tetraalkoxycalix[4]arenes Fixed in the Cone Conformation and Synthesis of New Cavitands
  作者：Arturo Arduini、Stefano Fanni、Giuseppe Manfredi、Andrea Pochini、Rocco Ungaro、Anna R. Sicuri、Franco Ugozzoli

  DOI：10.1021/jo00110a054

  日期：1995.3

  Regioselectivity of the formylation of tetraalkoxycalix[4]arene fixed in the cone conformation has been studied. Direct, diametrical (1,3) diformylation of calix[4]arenes having four chelating chains at the lower rim has been achieved. Simple tetraalkoxycalix[4]arenes produce a mixture of diametrical (1,3) and proximal (1,2) diformylated products. The (1,3) functionalized compounds have been used for the synthesis of double calix[4]arenes 12a,d linked via the upper rim. The residual mobility of these cone conformers is indicated by the X-ray crystal structure of compound 12d, which shows a flattened cone conformation, and by the reactive behavior of 1,3-bis(hydroxymethyl) derivatives 9a,d which give very distorted 1,3-bridged compounds 11a,d, through an intramolecular cyclization process.