5,17-dihydroxymethyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene | 136991-59-8

• 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-dihydroxymethyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
• 英文别名: 5,17-Bis(hydroxymethyl)-25,26,27,28-tetrakis(ethoxyethoxy)calix[4]arene；[25,26,27,28-Tetrakis(2-ethoxyethoxy)-17-(hydroxymethyl)-5-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-dodecaenyl]methanol
• CAS: 136991-59-8
• 化学式: C₄₆H₆₀O₁₀
• 分子量: 772.976
• InChiKey: NRNKJTRFNIAECT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 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：
  114
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  5,17-dihydroxymethyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene 在 sodium hydride 、 对甲苯磺酰氯 作用下， 以 乙二醇二甲醚 、 甲苯 为溶剂， 反应 48.0h， 以30%的产率得到28,29,30,31-Tetrakis(2-ethoxyethoxy)-26-oxahexacyclo[11.11.3.13,23.15,9.111,15.117,21]hentriaconta-1(24),2,5(31),6,8,11,13,15(30),17,19,21(29),23(28)-dodecaene
  参考文献：
  名称：

  Direct Regioselective Formylation of Tetraalkoxycalix[4]arenes Fixed in the Cone Conformation and Synthesis of New Cavitands

  摘要：

  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.

  DOI：

  10.1021/jo00110a054
• 作为产物：
  描述：

  25,26,27,28-tetra(ethoxyethoxy)-calix[4]arene 在 sodium tetrahydroborate 、 四氯化锡 作用下， 以 乙醇 、 氯仿 为溶剂， 生成 5,17-dihydroxymethyl-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
  参考文献：
  名称：

  Photolabile calixarene-based rosette

  摘要：

  一个基于模型的Calix[4]芳香烃醚罗赛特，携带两个交替的光解二硫烷基-羟甲基基团和两个苯并苯甲酸酯基团，被合成并显示出具有与外部敏化的母体二硫烷-苯甲醛加合物相当的光诱导断裂效率。关键词：光诱导电子转移，光解，Calixarene，二硫烷-羰基加合物。

  DOI：

  10.1139/v03-057

文献信息

• Synthesis and metal-binding properties of [60]fullerene-linked calix[4]arenes: an approach to ‘exohedral metallofullerenes’
  作者：Masaru Kawaguchi、Atsushi Ikeda、Seiji Shinkai

  DOI：10.1039/a707258i

  日期：——

  ‘Fullerenocalixarenes’ in which [60]fullerene is covalently linked through two ionophoric chains to a cone-calix[4]arene 1 or to a 1,3-alternate calix[4]arene 2 have been synthesized for the first time: although the absorption spectrum of 2 is scarcely changed upon addition of metal cations, that of 1 is affected by added Li+, Na+ and Ag+, indicating the formation of exohedral [60]fullerene–metal complexes.

  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。
• New Upper Rim Pyridine-Bridged Calix[4]arenes:  Synthesis and Complexation Properties toward Neutral Molecules and Ammonium Ions in Organic Media
  作者：Arturo Arduini、William M. MGregor、Andrea Pochini、Andrea Secchi、Franco Ugozzoli、Rocco Ungaro

  DOI：10.1021/jo960937b

  日期：1996.1.1

  of calix[4]arenes, diametrically bridged at the upper rim with pyridino systems, has been synthesized. The shape, rigidity, and chemical structure of the bridge influence the host-guest complexation properties of these systems in solution toward several neutral molecules having acidic C-H bonds. Additionally, selective complexation of methylammonium tosylate in comparison with other ammonium salts has

  合成了一系列新的杯芳烃[4]芳烃，它们在上缘与吡啶基体系径向连接。桥的形状，刚性和化学结构影响这些体系在溶液中朝着几个带有酸性CH键的中性分子的主客体络合特性。另外，已经观察到甲苯磺酸甲基铵与其他铵盐的选择性络合，并且该络合物的强度通过杯芳烃主体的吡啶部分上的p-取代基的电子给体能力而增强。主体5与丙二腈和硝基甲烷的内配合物的X射线晶体结构已得到解析，证实了与桥的硬氧和氮原子以及杯芳烃的软芳环形成特定的CH键。
• 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。
• 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。
• Gas-phase complexation of neutral molecules by upper rim bridged calix[4]arenes
  作者：A. Arduini、M. Cantoni、E. Graviani、A. Pochini、A. Secchi、A.R. Sicuri、R. Ungaro、M. Vincenti

  DOI：10.1016/0040-4020(94)00919-l

  日期：1995.1

  with molecular units bearing a xylyl or a 2,4-hexadiynyl mojety have been synthesized. The shape, rigidity and chemical structure of the bridge determine the host-guest complexation properties of these systems towards neutral molecules in the gas-phase.

  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。