1,4-bis(tosylate ethyloxy ethyloxy ethyl)benzene | 134881-73-5

• 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: 1,4-bis(tosylate ethyloxy ethyloxy ethyl)benzene
• 英文别名: 1,4-bis[2-(2-(2-(p-toluenesulfonylethoxy)-ethoxy)ethoxy)]benzene；1,4-bis[2-(2-(2-hydroxyethoxy)ethoxy)ethoxy]benzene ditosylate；2-[2-[2-[4-[2-[2-[2-(4-methylphenyl)sulfonyloxyethoxy]ethoxy]ethoxy]phenoxy]ethoxy]ethoxy]ethyl 4-methylbenzenesulfonate
• CAS: 134881-73-5
• 化学式: C₃₂H₄₂O₁₂S₂
• 分子量: 682.81
• InChiKey: AYKQXKIQTRSGHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.94
• 重原子数：
  46.0
• 可旋转键数：
  24.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  142.12
• 氢给体数：
  0.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  1,4-bis(tosylate ethyloxy ethyloxy ethyl)benzene 在 potassium carbonate 、 三氯乙酸 作用下， 以 乙腈 为溶剂， 反应 37.0h， 生成
  参考文献：
  名称：

  Self-Assembling Porphyrin [2]-Catenanes

  摘要：

  Using the concepts of self-assembly developed for the construction of topologically complex molecules such as [2]-catenanes and rotaxanes, the syntheses of several prophyrin-catenanes are described. The successful insertion of the porphyrin subunit into [2]-catenanes has resulted from the adaptation of previously devised template-directed syntheses based primarily on pi-pi interactions and C-H...O and C-H...pi and hydrogen bonding. Several hydroquinol containing ether chains were successfully synthesized and subsequently strapped across a porphyrin ring; the X-ray crystal structures of two such molecules which vary in the length of the ether chain are reported. These strapped porphyrins were found to complex paraquat with a parallel orientation of the hydroquinol, paraquat, and porphyrin rings. The complexation of paraquat (K-a 1955 and 1640 M(-1), Delta G degrees = -4.5 and -4.4 kcal mol(-1) for 9 and 11, respectively) by these strapped porphyrins led to their subsequent inclusion, using template-directed self-assembly, into structures which represent the first examples of porphyrin-containing [2]-catenanes. The catenanes were subsequently characterized by FAB-MS and thoroughly examined using dynamic H-1 NMR. In the case of the hydroquinol-containing catenanes, a dynamic process was observed in solution in which the bipyridinium subunits of the tetracation were exchanged between ''inside'' and ''outside'' environments (rotation around the hydroquinol ring axis). The diethylene glycol containing catenanes 14 and 15 were observed to maintain an orientation of the tetracation in which the bipyridinium subunits are parallel to the porphyrin ring. The length of the ether strap in these catenanes influenced the rotation rates of the tetracation macrocycles (50 and 80 times per second for 14 and 15 and 2500 and 1500 times per second for 16 and 17, respectively) at ambient temperature. However, in air the catenanes, the overall orientation of the tetracation,with bipyridinium and porphyrin rings coparallel, is retained in solution. As an extension of the original concepts, an analogous strapped porphyrin containing a naphthoquinol moiety was synthesized and found to complex paraquat with K-a = 21 000 M(-1) and Delta G degrees = -5.9 kcal mol(-1). The general applicability of the template-directed synthetic procedure developed for porphyrin catenane synthesis was illustrated by the successful isolation of the naphthalene containing porphyrin [2]-catenane 23 in 45% yield. Tetracation exchange processes similar to those for the hydroquinol catenanes were observed, along with an additional process which was found to be the decomplexation/complexation of the naphthalene ring in what is termed an ''out, turn around, and in again'' process similar to that occurring in nonporphyrinic naphthalene [2]-catenanes.

  DOI：

  10.1021/ja00090a029
• 作为产物：
  描述：

  对苯二酚 在 potassium tert-butylate 、 三乙胺 作用下， 以 二氯甲烷 、 叔丁醇 为溶剂， 反应 70.0h， 生成 1,4-bis(tosylate ethyloxy ethyloxy ethyl)benzene
  参考文献：
  名称：

  Anelli, Pier Lucio; Ashton, Peter R.; Spencer, Neil, Angewandte Chemie, 1991, vol. 103, # 8, p. 1052 - 1054

  摘要：

  DOI：

文献信息

• Self-Assembly and Dynamics of [2]- and [3]Rotaxanes with a Dinuclear Macrocycle Containing Reversible Os−N Coordinate Bonds
  作者：Sung-Youn Chang、Jeung Soon Choi、Kyu-Sung Jeong

  DOI：10.1002/1521-3765(20010618)7:12<2687::aid-chem26870>3.0.co;2-a

  日期：2001.6.18

  clipping process. Using threads 13a and 13b that contain two adipamide groups, more complicated systems have been investigated in which [2]rotaxane, [3]rotaxane, and free components are in equilibrium. Concentration- and temperature-dependent 1H NMR spectroscopic studies allowed the identification of all possible elements and the determination of their relative distributions in solution. For example

  使用包含弱可逆OsVI-N配位键的双核大环化合物2，研究了[2]-和[3]轮烷的自组装和平衡动力学。当大环化合物2与线程4a-e混合在一起时，它们都包含一个己二酰胺位点，但端基的大小不同，[2]假轮烷和轮烷样复合物立即形成，其缔合常数> 7 x 103M（- 1）在298 K的CDCl3中。通过2D-EXSY实验研究的交换动力学表明，复合物的组装和拆卸是通过两个不同的途径（滑动或截短）发生的，这取决于端基的大小。滑动途径主要是产生假轮烷样复合物的较小端基，而剪切途径是产生轮状烷类复合物的较大端基。在相同条件下，交换势垒（deltaG ++）对于4a是14.3 kcalmol（-1），对于4d是16.7 kcalmol（-1），表明滑动过程比剪切过程至少快一个数量级。使用包含两个己二酰胺基团的线13a和13b，研究了更复杂的系统，其中[2]轮烷，[3]轮烷和游离组分处于平衡状态。浓度和温度相关的1H
• Synthesis, properties, and interaction with paraquat of new fluorenonocrownophanes containing a hydroquinone fragment
  作者：N. G. Luk’yanenko、T. I. Kirichenko、A. Yu. Lyapunov、E. Yu. Kulygina、A. V. Mazepa

  DOI：10.1134/s1070428009020249

  日期：2009.2

  New crownophane family was synthesized containing fragments of 2,7-dioxyfluorenone and hydroquinone connected with residues of tri- and tetraethylene glycols. The formation of inclusion complexes of these ligands with paraquat was established by means of mass spectrometry (fast-atom bombardment), 1H NMR and electronic spectroscopy. The crownophane with a larger ring formed the more stable complex.

  合成了新的冠环烷族，其含有与三和四乙二醇残基连接的2，7-二氧芴酮和对苯二酚的片段。通过质谱（快速原子轰击），1 H NMR和电子光谱确定了这些配体与百草枯的包合物的形成。具有较大环的环冠烷形成更稳定的络合物。
• Synthesis and Self-Assembly of a Rigid Exotopic Bisphenanthroline Macrocycle: Surface Patterning and a Supramolecular Nanobasket
  作者：Venkateshwarlu Kalsani、Horst Ammon、Frank Jäckel、Jürgen P. Rabe、Michael Schmittel

  DOI：10.1002/chem.200305770

  日期：2004.11.5

  The synthesis and characterisation of a rigid nanoscale macrocycle with two exotopic phenanthroline binding sites is reported. Scanning tunnelling microscopy (STM) at the solid-liquid interface reveals the formation of highly ordered monolayers of macrocycles with dimensions that are in good agreement with the calculated structure. Using the HETPHEN concept several bisheteroleptic coordination complexes

  有两个exotopic菲咯啉结合位点的刚性纳米级大环的合成和表征的报告。固液界面的扫描隧道显微镜（STM）揭示了大环的高度有序的单分子层的形成，其尺寸与所计算的结构非常吻合。使用HETPHEN概念，在铜（I）离子存在的情况下，制备了几种与其他菲咯啉的抗细菌配位配合物和一个纳米级篮子组件。NMR光谱，质谱数据和元素分析指出了溶液中篮筐组件的三种不同异构体。准备了一个银筐，可以很容易地将其转换成铜类似物。电喷雾电离（ESI）-MS和分光光度法研究为组装过程提供了更多的机械原理。
• Cyclophanes with self-recognising components
  作者：Pier-Lucio Anelli、Masumi Asakawa、Peter R. Ashton、George R. Brown、Wayne Hayes、Oldrich Kocian、Santiago Rodr�guez Pastor、J. Fraser Stoddart、Malcolm S. Tolley、Andrew J. P. White、David J. Williams

  DOI：10.1039/c39950002541

  日期：——

  High dilution techniques have been employed to construct a series of charged flexible cyclophanes comprised of π-electron-rich hydroquinone and π-electron-deficient bipyridinium residues linked by polyether spacer units of varying length: significant conformational changes, leading to intramolecular and intermolecular interactions between the π-donors and π-acceptors, have been observed—as evidenced by X-ray crystallographic and variable temperature 1H NMR and 2D ROESY spectroscopic investigations—within the series of the cyclophanes both in the solid and solution states as a result of increasing the lengths of the polyether spacer units.

  我们采用高稀释技术构建了一系列带电柔性环烷，这些环烷由富含 π 电子的对苯二酚和缺乏 π 电子的联吡啶残基组成，并由不同长度的聚醚间隔单元连接：X 射线晶体学、变温 1H NMR 和 2D ROESY 光谱研究证明，随着聚醚间隔单元长度的增加，在固态和溶液态的环烷系列中，π 供体和π 受体之间的构象发生了重大变化，从而导致分子内和分子间的相互作用。
• Translational Isomerism in Some Two- and Three-Station [2]Rotaxanes
  作者：David B. Amabilino、Peter R. Ashton、Sue E. Boyd、Marcos Gómez-López、Wayne Hayes、J. Fraser Stoddart

  DOI：10.1021/jo9612584

  日期：1997.5.1

  The template-directed syntheses of three [2]rotaxanes are described. They all have dumbbell components, with both hydroquinone and resorcinol rings inserted into polyether chains terminated by tetraarylmethane stoppers, that become encircled during the key self-assembly processes by the tetracationic cyclophane, cyclobis(paraquat-p-phenylene), with its two pi-electron deficient bipyridinium units.

  描述了三种[2]轮烷的模板指导的合成。它们都具有哑铃成分，氢醌和间苯二酚环均插入四芳基甲烷塞终止的聚醚链中，在关键的自组装过程中被四阳离子环烷，环双（百草枯-对苯撑）及其两个pi-环包围。电子不足的联吡啶单元。通过低温（1）H NMR光谱已经证明，π电子缺陷的四阳离子环烷具有非常高的优先级，以位于这些分子穿梭中的氢醌环周围。