5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(benzyloxy)calix<4>arene | 135501-31-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(benzyloxy)calix<4>arene
• 英文别名: 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrabenzyloxycalix<4>arene；p-tert-Butylcalix<4>arene tetrabenzyl ether；25,26,27,28-tetrakis(benzyloxy)-p-t-butylcalix[4]arene；tert-butylcalix[4]arene tetra(benzyl ether)；5,11,17,23-tetra-t-butyl-25,26,27,28-tetrabenzyloxycalix[4]arene；p-tert-Butylcalix[4]arene tetrabenzyl ether；25,26,27,28-Tetrabenzyloxy-5,11,17,23-tert-butylcalix[4]arene；5,11,17,23-tetratert-butyl-25,26,27,28-tetrakis(phenylmethoxy)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
• CAS: 135501-31-4；135501-32-5；134309-06-1；85694-24-2
• 化学式: C₇₂H₈₀O₄
• 分子量: 1009.42
• InChiKey: PABYMJYBRZKWOY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  20.2
• 重原子数：
  76
• 可旋转键数：
  16
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(benzyloxy)calix<4>arene 在 碘代三甲硅烷 作用下， 以 氯仿 为溶剂， 反应 3.0h， 生成 25-benzyloxy-5,11,17,23-tetra-tert-butyl-26,27,28-trihydroxycalix[4]arene
  参考文献：
  名称：

  杯[4]芳烃单烷基醚的一般合成

  摘要：

  通过用等量的碘代甲基甲基硅烷在CHCl 3中处理易得的-（2）或二烷基醚（3），已经开发了一种首先通用且高收率合成杯[4]芳烃单烷基醚（4）的方法。

  DOI：

  10.1016/s0040-4020(01)96132-0
• 作为产物：
  描述：

  p-tert-butyl-1,3-dibenzyloxycalix[4]arene 在 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 生成 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(benzyloxy)calix<4>arene
  参考文献：
  名称：

  Calixarenes. 25. Conformations and structures of the products of arylmethylation of calix[4]arenes

  摘要：

  The arylmethylations of calix[4]arenes reported in this paper serve as companion pieces to an earlier study of the effects of reaction conditions and the structure of the derivatizing agent on the conformational outcome of the aroylation of calix[4]arenes. In contrast to the aroylation reaction, where a significant and predictable relation is observed between the para substituent of the aroyl chloride and the ratio of conformers formed, the arylmethylation reaction shows only a small and much less easily predictable dependence of the conformer ratio on the para substituent of the arylmethyl halide. Also, whereas the products of aroylation are the cone and/or 1,3-alternate conformers, those of arylmethylation are the cone and/or partial cone conformers. While no rationale has yet emerged to explain this difference, a study of the benzylation of dibenzyl and tribenzyl ethers of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrahydroxycalix[4]arene has established that the conformations of the tetraethers are not completely established until the third step in some cases and the fourth step in others.

  DOI：

  10.1021/jo00015a039

文献信息

• Easy and Selective Method for the Synthesis of Mono-, Di-, Tri-, Tetra-O-Arylmethyl-P-T-Butylcalix[4]Arenes
  作者：Yuanyuan Xie、Wang Xia

  DOI：10.3184/174751912x13371837407801

  日期：2012.7

  Mono-, di-, tri- and tetra-O-arylmethyl-p-t-butylcalix[4]arenes were synthesised respectively from p-t-butylcalix[4]arene and arylmethyl bromide through an easy and selective one-step reaction. Mono- and di-arylmethyl ethers of p-t-butylcalix[4]arenes were prepared using LiH as a base, while tri- and tetra-arylmethyl derivatives were afforded in the presence of Ba(OH)₂ and BaO. These methods are remarkable for excellent selectivity, mild reaction conditions, moderate to good yields and easy purification.

  以对-叔丁基钙[4]炔和芳基甲基溴为原料，通过简单而有选择性的一步反应，分别合成了单芳基甲基对叔丁基钙[4]炔、二芳基甲基对叔丁基钙[4]炔、三芳基甲基对叔丁基钙[4]炔和四芳基甲基对叔丁基钙[4]炔。以 LiH 为碱制备了对叔丁基钙[4]炔的单芳基甲基醚和二芳基甲基醚，而在 Ba(OH)2 和 BaO 的存在下则得到了三芳基甲基衍生物和四芳基甲基衍生物。这些方法具有极佳的选择性、温和的反应条件、中等至良好的产率和易于纯化的特点。
• An easy access to tetra-o-alkylated calix[4]arenes of cone conformation
  作者：István Bitter、Alajos Grün、Béla Ágai、László Tôke

  DOI：10.1016/0040-4020(95)00401-s

  日期：1995.7

  Fully O-alkylated calix[4]arenes have been synthesized by the alkylation of p-tertbutylcalix[4]arene and its 1,3-dialkylated derivatives in liquid-liquid phase-transfer catalytic process. 1H4 and 1H2R2 could effeciently be deprotonated by aqueous NaOH (50% w/w)-toluene system and alkylated with alkyl (aralkyl, allyl) halogens in good yields affording calix[4]arene tetraethers of cone conformation.

  通过对-叔丁基杯[4]芳烃及其1,3-二烷基化衍生物在液-液相转移催化过程中的烷基化反应，可以合成出完全O-烷基化的杯[4]芳烃。1H 4和1H 2 R 2可以用NaOH（50％w / w）甲苯水溶液有效地去质子化，并用烷基（芳烷基，烯丙基）卤素进行烷基化，收率很高，得到圆锥构象的杯[4]芳烃四醚。
• Silver Ion-Selective Electrodes Using π-Coordinate Calix[4]arene Derivatives as Soft Neutral Carriers
  作者：Keiichi Kimura、Setsuko Yajima、Kenta Tatsumi、Masaaki Yokoyama、Masatoshi Oue

  DOI：10.1021/ac000490d

  日期：2000.11.1

  as soft neutral carriers for silver ion sensors. Most of all, tert-butylcalix[4]arene tetra(allyl ether) is an excellent neutral carrier for plasticized poly(vinyl chloride)-membrane silver ion-selective electrodes. The ion sensors showed high silver ion selectivity over alkali metal ions and also good selectivity against other soft metal ions such as lead and mercury(II) ions. The electrode potential

  结合有π-配位取代基（例如烯丙基，苄基和炔丙基）的杯[4]芳烃衍生物被设计为银离子传感器的软中性载体。最重要的是，叔丁基杯[4]亚芳基四烯丙基醚是用于增塑聚氯乙烯-膜银离子选择电极的优良中性载体。离子传感器对碱金属离子具有很高的银离子选择性，并且对其他软金属离子（如铅和汞（II）离子）具有良好的选择性。由于π-配位取代基和银离子之间的软相互作用，电极电势响应与中性载体型碱金属离子电极一样快，这通过1H NMR光谱得以阐明。
• Calixarenes 9
  作者：C.David Gutsche、Balram Dhawan、Jeffrey A. Levine、Kwang Hyun No、Lorenz J. Bauer

  DOI：10.1016/s0040-4020(01)88541-0

  日期：1983.1

  Calix[4]arene (1A), p-t-butylcalix[4]arene (1B), and p-allylcalix[4]arene (1C) have been converted to various derivatives, including the methyl, ethyl, allyl, benzyl and trimethylsilyl ethers and the acetates. Although the parent calixarenes exist preferentially in the cone conformation, they are conformationally flexible and at room temperature interconvert at a rate of ca 100 sec−1. All but the methyl

  杯[4]芳烃（1A），对叔丁基杯[4]芳烃（1B）和对-烯丙基[4]芳烃（1C）已转化为各种衍生物，包括甲基，乙基，烯丙基，苄基和三甲基甲硅烷基醚和乙酸酯。尽管亲本杯芳烃优先存在于圆锥构象中，但它们构象灵活，并且在室温下以约100 sec -1的速率相互转化。另一方面，除甲基醚外，所有醚在室温下均呈构象刚性。在大多数情况下，优选的构型是视锥和部分视锥，这取决于形成的衍生物（即甲基和乙基醚偏爱部分视锥；苄基和三甲基甲硅烷基醚偏爱视锥）。在烯丙基醚和乙酸酯的情况下，对位取代基似乎会影响构象结果（即1A和1B分别形成部分圆锥和圆锥构象的烯丙基醚；1A和1B分别形成1,3-交替和部分圆锥构象的乙酸盐）。圆锥和部分圆锥构象中的构象刚性杯芳烃衍生物属于一小组合成化合物，这些化合物包含一个永久性空腔（“不变杯”），该空腔的大小足以包封其他分子。
• On the Origin of the Distal vs. Proximal Regioselectivity in Di-<i>O</i>-alkylation of Calix[4]arenes
  作者：Koji Araki、Koji Iwamoto、Satoshi Shigematsu、Seiji Shinkai

  DOI：10.1246/cl.1992.1095

  日期：1992.6

  basis of the distal vs. proximal regioselectivity in di-O-alkylation of calix[4]arene was investigated through the detailed product analyses. It was found that (i) the regioselectivity is profoundly affected by the residual intramolecular hydrogen-bonds and (ii) the distal isomer is more reactive for further O-alkylation than the proximal isomer, resulting in the “apparent” proximal selectivity.

  通过详细的产物分析研究了杯[4]芳烃二-O-烷基化中远端与近端区域选择性的机制基础。发现（i）区域选择性受残留分子内氢键的影响很大，（ii）远端异构体比近端异构体对进一步的 O-烷基化更具反应性，导致“表观”近端选择性。