3-iodo-5-ethynyl-1-tert-butylbenzene | 167319-35-9

• 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: 3-iodo-5-ethynyl-1-tert-butylbenzene
• 英文别名: 1-Tert-butyl-3-ethynyl-5-iodobenzene
• CAS: 167319-35-9
• 化学式: C₁₂H₁₃I
• 分子量: 284.14
• InChiKey: OJJDNNIETJYVJF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  3,5-diazido-1-(tert-butyl)benzene 、 3-iodo-5-ethynyl-1-tert-butylbenzene 在 copper(II) sulfate 、 Erythorbic acid 作用下， 以 乙醇 、 水 、 甲苯 为溶剂， 以91%的产率得到1,1'-(5-(tert-butyl)-1,3-phenylene)bis(4-(3-(tert-butyl)-5-iodophenyl)-1H-1,2,3-triazole)
  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
• 作为产物：
  描述：

  3-iodo-1-tert-butyl-5-(trimethylsilylethynyl)benzene 在 potassium fluoride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 8.0h， 生成 3-iodo-5-ethynyl-1-tert-butylbenzene
  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

• Macrocycle Size Matters: “Small” Functionalized Rotaxanes in Excellent Yield Using the CuAAC Active Template Approach
  作者：Hicham Lahlali、Kajally Jobe、Michael Watkinson、Stephen M. Goldup

  DOI：10.1002/anie.201100415

  日期：2011.4.26

  the CuAAC active template reaction not only is it demonstrated to be possible to use smaller macrocycles, but, surprisingly, that smaller macrocycles lead to higher yields of rotaxane product (see scheme). The synthesis of “small” functionalized [2]rotaxanes showcases this as a method for the production of materials with potential applications in molecular electronics, drug delivery, sensing, and enantioselective

  通过缩小CuAAC活性模板反应中的大环，不仅证明可以使用较小的大环，而且令人惊讶的是，较小的大环可导致轮烷产品的更高收率（参见方案）。“小的”功能化[2]轮烷的合成证明这是一种生产材料的方法，在分子电子学，药物输送，传感和对映选择性催化方面具有潜在的应用前景。
• Pure CH Hydrogen Bonding to Chloride Ions: A Preorganized and Rigid Macrocyclic Receptor
  作者：Yongjun Li、Amar H. Flood

  DOI：10.1002/anie.200704717

  日期：2008.3.25