5,17-dibromo-25,26,27,28-tetrahydroxycalix[4]arene | 195323-68-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 5,17-dibromo-25,26,27,28-tetrahydroxycalix[4]arene
• 英文别名: 5,17-Dibromopentacyclo[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-25,26,27,28-tetrol
• CAS: 195323-68-3
• 化学式: C₂₈H₂₂Br₂O₄
• 分子量: 582.288
• InChiKey: WQESWRXXQQFZFW-UHFFFAOYSA-N

物化性质

• 熔点：
  341-343 °C
• 沸点：
  663.7±55.0 °C(Predicted)
• 密度：
  1.625±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  34
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  80.9
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,17-dibromo-25,26,27,28-tetrahydroxycalix[4]arene 在 1,1'-双(二苯基膦)二茂铁 、 tris(dibenzylideneacetone)dipalladium (0) sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 144.0h， 生成 5,17-dicyano-25,26,27,28-tetra(ethoxyethoxy)-calix[4]arene
  参考文献：
  名称：

  Hioki; Nakaoka; Maruyama, Journal of the Chemical Society. Perkin Transactions 1 (2001), 2001, # 24, p. 3265 - 3268

  摘要：

  DOI：
• 作为产物：
  描述：

  杯[4]芳烃 在 sodium hydroxide 、 溴 、 potassium carbonate 作用下， 以 四氢呋喃 、 氯仿 、 水 、 乙腈 为溶剂， 生成 5,17-dibromo-25,26,27,28-tetrahydroxycalix[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。
• Information transfer in calix[4]arenes: influence of upper rim substitution on alkaline metal complexation at the lower rim
  作者：Daniel T. Schühle、Sascha Klimosch、Jürgen Schatz

  DOI：10.1016/j.tetlet.2008.07.128

  日期：2008.9

  Novel calix[4]arene amides have been synthesized and their interaction with alkaline cations has been evaluated through extracting aqueous solutions of Li-, Na- and K-picrates with solutions of calix[4]arene amides in CH2Cl2. Electron-withdrawing groups on the upper rim of the calix[4]arene scaffold were found to have a negative effect on the absolute amount of metal ions extracted. The decreased extraction

  合成了新型杯[4]芳烃酰胺，并用杯[4]芳烃酰胺在CH 2 Cl 2中的溶液萃取了Li-，Na-和K-苦味酸盐的水溶液，评估了它们与碱性阳离子的相互作用。杯[4]芳烃支架上缘的吸电子基团对提取的金属离子的绝对量具有负面影响。降低的萃取能力伴随着对钠阳离子的更高选择性。
• Synthesis of polyfunctional phosphorus-containing calixarenes in cycloaddition reactions of azides to alkynes
  作者：Nikita A. Drigo、Alexander N. Gorbunov、Dmitry N. Gorbunov、Marta Yu. Talanova、Yulia S. Kardasheva、Vladimir V. Kovalev、Anton L. Maximov、Ivan M. Vatsouro

  DOI：10.1007/s10593-017-2005-0

  日期：2016.12

  phosphoruscontaining calixarenes and the ratio of spatial isomers in the exaustively alkylated products was studied. The reduction of phosphine oxide groups and modification of functional groups in the triazole rings were used for the synthesis of bulky hydrophilic phosphinecontaining ligands. The catalytic activity of in situ obtained rhodium complexes of phosphine-containing calixarenes was preliminarily studied

  杯[4]芳烃的单和二溴衍生物首次用于磷酸化，烷基化和叠氮-炔烃环加成序列，以便合成在上缘和1,4-二取代的三唑环上含有氧化膦基团的多官能大环在下缘。研究了反应条件对含磷杯芳烃低缘烷基化反应的选择性以及精细烷基化产物中空间异构体比例的影响。三唑环中的氧化膦基团的还原和官能团的修饰用于合成大体积的亲水性含膦的配体。原位催化活性 通过1-辛烯加氢甲酰化在乙醇中初步研究了所得的含膦杯芳烃的铑配合物。
• 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
• 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.