1-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-3,5-diazidobenzene | 1044811-15-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-3,5-diazidobenzene
• 英文别名: 1,3-diazido-5-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)benzene；1,3-Diazido-5-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]benzene
• CAS: 1044811-15-5
• 化学式: C₁₃H₁₈N₆O₄
• 分子量: 322.324
• InChiKey: DQBBTXAASTWFLU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  23
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  65.6
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-3,5-diazidobenzene 、 2-ethynyl-6-(2-(trimethylsilyl)ethynyl)pyridine 在 copper(II) sulfate 、 sodium ascorbate 作用下， 以 乙醇 、 水 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  Dipole-Promoted and Size-Dependent Cooperativity between Pyridyl-Containing Triazolophanes and Halides Leads to Persistent Sandwich Complexes with Iodide

  摘要：

  Triazolophanes that incorporate pyridyl subunits in place of phenylenes show a heightened propensity to form 2:1 sandwich complexes with halides. Persistent iodide-based sandwiches are observed. Binding constants confirm that the inward-facing electron pairs on the pyridyls destabilize the 1:1 complexes with halides. The H-1 NMR spectra verify that the sandwich complexes have two TT-stacked triazolophanes rotated to allow registration between opposite dipoles on the pyridyls (directed inward) and triazoles (directed outward). These dipolar interactions cooperate to lower the pyridyl-based repulsions, therefore, increasing K-2. Modest cooperative effects are observed for the snugly fitting F-, Cl-, and Br- halides while the too-large l(-) shows highly positive cooperativity.

  DOI：

  10.1021/ja8077329
• 作为产物：
  描述：

  1-(2-(2-(2-甲氧基乙氧基)乙氧基)乙氧基)-3,5-二碘苯 在 copper(l) iodide 、 sodium azide 、 Erythorbic acid 、 N,N'-二甲基乙二胺 作用下， 以 水 、 二甲基亚砜 为溶剂， 以85%的产率得到1-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-3,5-diazidobenzene
  参考文献：
  名称：

  Strong, Size-Selective, and Electronically Tunable C−H···Halide Binding with Steric Control over Aggregation from Synthetically Modular, Shape-Persistent [3₄]Triazolophanes

  摘要：

  A series of shape-persistent [3(4)]triazolophanes bearing t-butyl or triethylene glycol (OTg) substituents on the phenylene linkers have been prepared in a modular manner from simple building blocks. Triazolophane-halide binding affinities were determined using UV titrations in order to help in understanding the driving forces behind the large receptor-anion binding strengths supported solely by CH hydrogen-bond donors. The fixed size of the central cavity provides a means for selective recognition of Cl- and Br- anions with large binding strengths (K-a > 1 000 000 M-1; Delta G > -8.5 kcal mol(-1)). The smaller F- and larger I- anions are bound less tightly by similar to 1 and similar to 3 orders of magnitude, respectively. The four triazole-based H-bond donors are believed to be of primary importance, while the four phenylene CH H-bond donors take on a secondary role. Consistent with this idea, the binding affinity can be tuned by as much as 1 kcal mol-1 by changing the character of the four phenylene-based substituents from more (OTg) to less (t-butyl) electron-donating. Preorganization was also found to play a central role, on the basis of comparisons with a foldamer analogue that shows much-reduced binding. Aggregation was facilitated as the substituents were changed from t-butyl to OTg, increasing the degree of self-association from K-E approximate to 0 to 230 M-1 in CD2Cl2. Diffusion NMR experiments established aggregation as opposed to dimerization. These findings indicate the importance of the cavity size for selective anion recognition as well as the role of the phenylene linkers in tuning the binding strengths and modulating the aggregation of the [3(4)]triazolophanes.

  DOI：

  10.1021/ja803341y

文献信息

• [EN] CONTROLLING CONCENTRATIONS OF ANIONS WITH LIGHT USING ARYL-TRIAZOLE FOLDAMERS<br/>[FR] CONTRÔLE DE CONCENTRATIONS D'ANIONS AVEC DE LA LUMIÈRE EN UTILISANT DES FOLDAMÈRES D'ARYL-TRIAZOLE
  申请人：INDIANA RES & TECHNOLOGY CORP

  公开号：WO2012024029A1

  公开（公告）日：2012-02-23

  The invention provides novel aryl-triazole foldamers and methods for changing the concentration of anions using said foldamers.

  这项发明提供了新型芳基三唑折叠聚合物以及利用这些折叠聚合物改变阴离子浓度的方法。
• Flipping the Switch on Chloride Concentrations with a Light-Active Foldamer
  作者：Yuran Hua、Amar H. Flood

  DOI：10.1021/ja105793c

  日期：2010.9.22

  wavelength-dependent release and then reuptake of chloride ions in nonaqueous solutions. A chiral aryl-triazole foldamer with two azobenzene end groups has been synthesized to define a folded binding pocket for chloride ions that unfolds with UV light to liberate the chloride. The trans-dominated helical foldamer becomes less stable upon photoisomerization to the cis forms. Simultaneously, the observed binding

  在这里，我们展示了一个仿生系统，其中光刺激用于触发波长依赖性释放，然后再吸收非水溶液中的氯离子。已经合成了具有两个偶氮苯端基的手性芳基-三唑折叠体来定义氯离子的折叠结合袋，氯离子在紫外光下展开以释放氯。在光异构化为顺式形式后，反式主导的螺旋折叠体变得不太稳定。同时，观察到的结合亲和力从 K = 3000 M(-1) (MeCN, 298 K) 降低了约 10 倍。通过上下切换电解质溶液的电导率来证明使用光控制氯化物水平。
• An Overlooked yet Ubiquitous Fluoride Congenitor: Binding Bifluoride in Triazolophanes Using Computer-Aided Design
  作者：Raghunath O. Ramabhadran、Yun Liu、Yuran Hua、Moira Ciardi、Amar H. Flood、Krishnan Raghavachari

  DOI：10.1021/ja500125r

  日期：2014.4.2

  Despite its ubiquity during the binding and sensing of fluoride, the role of bifluoride (HF2-) and its binding properties are almost always overlooked. Here, we give one of the first examinations of bifluoride recognition in which we use computer-aided design to modify the cavity shape of triazolophanes to better match with HF2-. Computational investigation indicates that HF2- and cr should have similar binding affinities to the parent triazolophane in the gas phase. Evaluation of the binding geometries revealed a preference for binding of the linear HF2- along the north-south axis with a smaller Boltzmann weighted population aligned east-west and all states being accessed rapidly through in-plane precessional rotations of the anion. While the 'H NMR spectroscopy studies are consistent with the calculated structural aspects, binding affinities in solution were determined to be significantly smaller for the bifluoride than the chloride. Computed geometries suggested that a 20 tilting of the bifluoride (stemming from the cavity size) could account for the 25-fold difference between the two binding affinities, HF2- < Cl- Structural variations to the triazolophane's geometry and electronic modifications to the network of hydrogen bond donors were subsequently screened in a stepwise manner using density functional theory calculations to yield a final design that eliminates the tilting. Correspondingly, the bifluoride's binding affinity (K 10(6) M-1) increased and was also found to remain equal to chloride in the gas and solution phases. The new oblate cavity appeared to hold the HF2- in a single east-west arrangement. Our findings demonstrate the promising ability of computer-aided design to fine-tune the structural and electronic match in anion receptors as a means to control the arrangement and binding strength of a desired guest.