3-ethynyl-4-triisopropylsilylethynylpyridine | 860021-85-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 3-ethynyl-4-triisopropylsilylethynylpyridine
• 英文别名: 2-(3-Ethynylpyridin-4-yl)ethynyl-tri(propan-2-yl)silane
• CAS: 860021-85-8
• 化学式: C₁₈H₂₅NSi
• 分子量: 283.489
• InChiKey: ABAKWVFGSLKMGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.63
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-ethynyl-4-triisopropylsilylethynylpyridine 在 bis-triphenylphosphine-palladium(II) chloride 吡啶 、 copper(l) iodide 、 氧气 、 potassium carbonate 、 三乙胺 、 copper(l) chloride 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 193.5h， 生成 1,4-bis[2-({4-[(triisopropylsilyl)ethynyl]pyridin-3-yl}ethynyl)phenyl]buta-1,3-diyne
  参考文献：
  名称：

  Nitrogen Heterocyclic Carbon-Rich Materials:  Synthesis and Spectroscopic Properties of Dehydropyridoannulene Macrocycles

  摘要：

  A new series of nitrogen heterocyclic dehydroannulenes 1-3 have been synthesized and their macrocyclic structures assigned using spectroscopic methods. The chiral and planar ground state conformations of 1 and 3, respectively, were determined by semiempirical theoretical calculations. All dehydropyridoannulenes and precursors possessing four aromatic rings functioned as fluorescent chromophores. A detailed spectroscopic investigation into the cation-binding properties of 3 in dilute solution revealed a particularly selective photoluminescence quenching sensory response for Pd-II ions. Cycle 3, as well as 1 and 2, also exhibited reversible proton-triggered luminescence quenching behavior. At higher concentrations, 3 afforded a coordination polymer precipitate with Ag-I ions. Cycles I and 2 and precursors 15, 23, and 29 also undergo thermochemical reactions that may potentially lead to carbon-rich polymers. The physicochemical properties of 1-3 suggest that dehydropyridoarmulenes may serve as a particularly versatile new class of ligands for the creation of novel heteroatom-containing carbon-rich materials with many potential applications in supramolecular materials science and nanotechnology.

  DOI：

  10.1021/jo040276f
• 作为产物：
  描述：

  3-bromo-4-(triisopropylsilylethynyl)pyridine 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 正丁基锂 、 potassium carbonate 、 三乙胺 作用下， 以 甲醇 、 乙醚 、 正己烷 为溶剂， 反应 24.5h， 生成 3-ethynyl-4-triisopropylsilylethynylpyridine
  参考文献：
  名称：

  Nitrogen Heterocyclic Carbon-Rich Materials:  Synthesis and Spectroscopic Properties of Dehydropyridoannulene Macrocycles

  摘要：

  A new series of nitrogen heterocyclic dehydroannulenes 1-3 have been synthesized and their macrocyclic structures assigned using spectroscopic methods. The chiral and planar ground state conformations of 1 and 3, respectively, were determined by semiempirical theoretical calculations. All dehydropyridoannulenes and precursors possessing four aromatic rings functioned as fluorescent chromophores. A detailed spectroscopic investigation into the cation-binding properties of 3 in dilute solution revealed a particularly selective photoluminescence quenching sensory response for Pd-II ions. Cycle 3, as well as 1 and 2, also exhibited reversible proton-triggered luminescence quenching behavior. At higher concentrations, 3 afforded a coordination polymer precipitate with Ag-I ions. Cycles I and 2 and precursors 15, 23, and 29 also undergo thermochemical reactions that may potentially lead to carbon-rich polymers. The physicochemical properties of 1-3 suggest that dehydropyridoarmulenes may serve as a particularly versatile new class of ligands for the creation of novel heteroatom-containing carbon-rich materials with many potential applications in supramolecular materials science and nanotechnology.

  DOI：

  10.1021/jo040276f

文献信息

• Electronic, Spectroscopic, and Ion-Sensing Properties of a Dehydro[<i>m</i>]pyrido[14]- and [15]annulene Isomer Library
  作者：Paul N. W. Baxter、Abdelaziz Al Ouahabi、Jean-Paul Gisselbrecht、Lydia Brelot、Alexandre Varnek

  DOI：10.1021/jo201595s

  日期：2012.1.6

  An isomeric series of dehydro[m]pyrido[n]annulenes incorporating strained 1,4-buta-1,3-diyne units have been synthesized, where m = 2, n = 14 (1a–d); m = 2, n = 15 (2a,b); and m = 3, n = 15 (3). The number of pyridine rings and annulene ring π-electrons are denoted by m and n, respectively. The X-ray crystal structures of 1b and 1c confirmed their cyclic formulation. All macrocycles were found to be

  合成了一个含有一系列应变的1,4-丁1,3-二炔单元的脱氢[ m ]吡啶基[ n ]环烯异构体，其中m = 2，n = 14（1a – d）；m = 2，n = 15（2a，b）；并且m＝ 3，n＝ 15（3）。吡啶环和环的π电子数分别由m和n表示。1b和1c的X射线晶体结构证实了他们的循环配方。发现所有大环化合物都是发光发色团，具有不同的异构体依赖性质子和金属离子感应发射响应，这些响应共同以分析物特定的颜色模式显示。在所研究的系列中，1a在显示最高的发光量子产率方面是奇异的，并且在质子化和与Hg II结合时具有最强的发射能量和摩尔吸收变化。光谱和电化学结果得到密度泛函理论计算的支持，如图1a，2a和3所示。成为低带隙的材料，其最低的未占据分子轨道在1,4-二（吡啶-4-基）丁1,3-二炔桥上离域，这些桥为氮之间的电子通信提供了途径。总体而言，研究表明1a，2a和3将是用于构建新型共轭杂化
• An Investigation into the Stephens-Castro Synthesis of Dehydrotriaryl[12]annulenes: Factors Influencing the Cyclotrimerization
  作者：Paul N. W. Baxter、Abdelaziz Al Ouahabi、Lydia Karmazin、Alexandre Varnek、Jean-Marc Strub、Sarah Cianferani

  DOI：10.1002/ejoc.201901053

  日期：2019.10.31

  An exploration of the reaction conditions under which the Stephens–Castro reaction of o‐iodoarylethynylcuprates 6 and 8 preferentially afford macrocyclic dehydrotriaryl[12]annulenes 1 and 2 rather than giving polymeric products, suggest a mechanism that involves initial assembly of the ethynylcuprates into a soluble oligonuclear structure preorganized for cyclotrimerization.

  对反应条件的探索，在该条件下，邻碘芳基乙炔基乙酸铜6和8的斯蒂芬斯–卡斯特罗反应优先提供大环脱氢​​三芳基[12]环戊烯1和2而不是提供聚合产物，这提示了一种机理，该方法涉及乙炔基乙酸酯的初始组装为可溶物。预先为环三聚而组织的寡核结构。