5,17-dibromo-26,28-dibenzoyloxy-calix[4]arene | 392743-36-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5,17-dibromo-26,28-dibenzoyloxy-calix[4]arene
• 英文别名: (27-Benzoyloxy-5,17-dibromo-26,28-dihydroxy-25-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) benzoate；(27-benzoyloxy-5,17-dibromo-26,28-dihydroxy-25-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) benzoate
• CAS: 392743-36-1
• 化学式: C₄₂H₃₀Br₂O₆
• 分子量: 790.505
• InChiKey: OKMLNCIYALNVQU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.2
• 重原子数：
  50
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  93.1
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5,17-dibromo-26,28-dibenzoyloxy-calix[4]arene 在 sodium hydroxide 、 sodium hydride 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 5,17-dibromo-25,26,27,28-tetra-n-propylcalix[4]arene
  参考文献：
  名称：

  Regioselective upper-rim functionalizations of calix[4]arene by diphenylphosphino groups

  摘要：

  对calix[4]arene的上缘选择性官能化已经进行，以制备所有多取代二苯基膦衍生物。此外，已确定了5,17-二溴-11,23-双(二苯基膦基)-25,26,27,28-四-n-丙氧基calix[4]arene和5,11,17,23-四(二苯基膦基)-25,26,27,28-四异丙氧基calix[4]arene的X射线结构。通过适当选择碱、烷基锂-溶剂系统、化学计量、反应时间等方法实现了选择性官能化。开发了一种新的便捷方法，可在相对较大规模上选择性地制备calix[4]arenes的衍生物，涉及将远端二酯衍生物转酯化为近端异构体。关键词：calix[4]arenes、膦、上缘、X射线结构、转酯化。

  DOI：

  10.1139/v01-161
• 作为产物：
  描述：

  25,27-dibenzoyloxy-26,28-dihydroxycalix[4]arene 在 溴 作用下， 以 氯仿 为溶剂， 以96%的产率得到5,17-dibromo-26,28-dibenzoyloxy-calix[4]arene
  参考文献：
  名称：

  Regioselective upper-rim functionalizations of calix[4]arene by diphenylphosphino groups

  摘要：

  对calix[4]arene的上缘选择性官能化已经进行，以制备所有多取代二苯基膦衍生物。此外，已确定了5,17-二溴-11,23-双(二苯基膦基)-25,26,27,28-四-n-丙氧基calix[4]arene和5,11,17,23-四(二苯基膦基)-25,26,27,28-四异丙氧基calix[4]arene的X射线结构。通过适当选择碱、烷基锂-溶剂系统、化学计量、反应时间等方法实现了选择性官能化。开发了一种新的便捷方法，可在相对较大规模上选择性地制备calix[4]arenes的衍生物，涉及将远端二酯衍生物转酯化为近端异构体。关键词：calix[4]arenes、膦、上缘、X射线结构、转酯化。

  DOI：

  10.1139/v01-161

文献信息

• Regioselective upper-rim functionalizations of calix[4]arene by diphenylphosphino groups
  作者：Jonathan Gagnon、Martin Vézina、Marc Drouin、Pierre D Harvey

  DOI：10.1139/v01-161

  日期：2001.10.1

  The regioselective upper-rim functionalization of calix[4]arene have been performed to prepare all the multisubstituted diphenylphosphine derivatives. In addition, the X-ray structures of 5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene and 5,11,17,23-tetrakis(diphenylphosphino)-25,26,27,28-tetra-i-propoxy-calix[4]arene have been determined. Regioselective functionalizations have been achieved using methods that involve appropriate choices of bases, alkyllithium-solvent systems, stoichiometry, and reaction times. A new and convenient method for selectively preparing derivitized calix[4]arenes at proximal positions in relative large scale quantity has been developed and involves a transesterification of the distal diester derivative into the proximal isomer.Key words: calix[4]arenes, phosphine, upper-rim, X-ray structure, transesterification.

  对calix[4]arene的上缘选择性官能化已经进行，以制备所有多取代二苯基膦衍生物。此外，已确定了5,17-二溴-11,23-双(二苯基膦基)-25,26,27,28-四-n-丙氧基calix[4]arene和5,11,17,23-四(二苯基膦基)-25,26,27,28-四异丙氧基calix[4]arene的X射线结构。通过适当选择碱、烷基锂-溶剂系统、化学计量、反应时间等方法实现了选择性官能化。开发了一种新的便捷方法，可在相对较大规模上选择性地制备calix[4]arenes的衍生物，涉及将远端二酯衍生物转酯化为近端异构体。关键词：calix[4]arenes、膦、上缘、X射线结构、转酯化。
• Synthesis of 1,3-diketo derivatives of calix[4]arene with nonyl substituents at the lower rim as novel efficient sensibilizers of Tb3+ luminescence
  作者：S. N. Podyachev、G. Sh. Gimazetdinova、S. N. Sudakova、D. V. Lapaev、V. V. Syakaev、R. N. Nagimov

  DOI：10.1134/s1070363217090110

  日期：2017.9

  Novel bis- and tetra-1,3-diketo derivatives of calix[4]arene with nonyl substituents at the lower rim have been synthesized. Their conformational and tautomeric composition have been determined; spectral parameters and complex formation properties with Tb3+ have been studied. Substitution of two 1,3-diketo groups with bromine under going from tetra- to bis 1,3-diketone derivatives was resulted in twofold increase luminescence intensity in their terbium complexes. Lifetime of the excited state of the terbium luminescence of the corresponding complexes as well as lifetime of excited triplet level of the 1,3-diketonate ligands have been determined.
• Influence of upper rim dibromo-substitution in bis-1,3-diketone calix[4]arenes on spectral properties of ligands and their lanthanide complexes
  作者：Sergey N. Podyachev、Gulnaz Sh. Gimazetdinova、Svetlana N. Sudakova、Nataliya A. Shamsutdinova、Dmitry V. Lapaev、Victor V. Syakaev、Aidar T. Gubaidullin、Rinas N. Nagimov、Asiya R. Mustafina

  DOI：10.1016/j.tet.2017.07.043

  日期：2017.9

  rim as ligands for Gd3+ and Tb3+ complexes. The dibromo-substitution does not affect 1:1 complex formation with the lanthanide ions arising from their coordination via two 1,3-diketonate groups incorporated at the upper rim of the calix[4]arene. The analysis of the time-resolved luminescence spectra of the Gd3+ complexes clearly demonstrates the notable enhancement of the decay time of the ligand triplet

  本工作介绍了上边缘二溴取代的双-1,3-二酮杯[4]芳烃的合成和表征，该芳烃在下边缘具有羟基和丙氧基作为Gd 3+和Tb 3+配合物的配体。二溴取代不会影响镧系元素离子的1：1络合物形成，而镧系元素离子是通过在杯[4]芳烃的上边缘结合的两个1,3-二酮酸酯基团进行配位而形成的。Gd 3+的时间分辨发光光谱分析配合物清楚地证明了配体三重态衰变时间的显着延长，而新的二溴-双-1,3-二酮的三重态能量与其未取代的类似物相比实际上保持不变。后一种趋势表明，重原子效应对从激发态到二溴取代的配体的振动能级的能量转移产生影响，导致无辐射衰变贡献降低。Tb 3+中心发光的测量结果表明，二溴杯[4]芳烃与其未取代的对应物相比，具有更好的触角效应（约1.7）。
• A clip-like host that undergoes self-assembly and competitive guest-induced disassembly in water
  作者：Meagan A. Beatty、Jil A. Busmann、Noah G. Fagen、Graham A. E. Garnett、Fraser Hof

  DOI：10.1080/10610278.2018.1494275

  日期：2019.3.4

  ABSTRACT Certain calix[4]arenes that are anionic and appended with a single hydrophobic substituent can self-assemble into homodimers in water. The unusual behaviours of these assemblies in water solutions are largely attributed to them being formed from like-charged building blocks. We report here a new entry into this series – a difunctionalized analog with two hydrophobic arms, a net – 3 charge

  摘要 某些带有单个疏水取代基的阴离子杯[4]芳烃可以在水中自组装成同型二聚体。这些组件在水溶液中的异常行为很大程度上归因于它们是由带相同电荷的积木形成的。我们在此报告该系列的一个新条目——具有两个疏水臂的双官能化类似物、每个单体上有一个净 3 个电荷，以及一个整体的 U 形“夹子”拓扑结构。我们使用 1H NMR、1-D DOSY 和 ITC 来表明新化合物在水中二聚化，但在有机溶剂中保持单体。各种阳离子铵离子客体能够驱动二聚体分解，有利于 1:1 的主客体复合物。竞争程度与整体客体疏水性成正比。图形概要