4-(1,3-丁二炔-1-基)吡啶 | 176715-52-9

• 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
• 中文名称: 4-(1,3-丁二炔-1-基)吡啶
• 英文名称: 4-(buta-1,3-diynyl)pyridine
• 英文别名: 4-(1,3-butadiynyl)pyridine；(4-pyridyl)-1,3-butadiyne；4-Buta-1,3-diynylpyridine
• CAS: 176715-52-9
• 化学式: C₉H₅N
• mdl: MFCD18804185
• 分子量: 127.145
• InChiKey: XZIQPDVMFOZALA-UHFFFAOYSA-N

物化性质

• 沸点：
  216.5±22.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  4-(1,3-丁二炔-1-基)吡啶 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以31%的产率得到1,8-di(pyridin-4-yl)octa-1,3,5,7-tetrayne
  参考文献：
  名称：

  Oligoyne Single Molecule Wires

  摘要：

  We report the electrical conductance at the single molecule level of the oligoyne molecular wires Py-(C C)(n)-Py (n = 1, 2 and 4; Py = 4-pyridyl) using STM-molecular break junction techniques in Au vertical bar molecule vertical bar Au configurations. The conductance histograms reveal multiple series of peaks attributed to differing contact geometries between the pyridyl head groups and the gold electrodes. Both experimental and theoretical evidence point to the higher conduction groups being related to adsorption of the pyridyl group at more highly coordinated sites such as step edges or alongside gold adatoms. All three conduction groups in the oligoyne series show a remarkably low beta value of (0.06 +/- 0.03) angstrom(-1), that is, the conductance is almost independent of molecular length. 4,4'-Bipyridyl studied under the same conditions does not follow this exponential decay series. Theoretical calculations using a combination of density functional theory and nonequilibrium Green's function formalism support the experimental results. We conclude that oligoynes and polyynes are a very promising class of molecular wires for integration into electronic circuitry.

  DOI：

  10.1021/ja9061129
• 作为产物：
  描述：

  4-碘吡啶 在 bis-triphenylphosphine-palladium(II) chloride sodium hydroxide 、 copper(l) iodide 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 18.0h， 生成 4-(1,3-丁二炔-1-基)吡啶
  参考文献：
  名称：

  芳基丁二烯终端稳定吗？一系列芳基和杂芳基-丁二炔（Ar-C⋮C-C⋮C-H）的合成和X射线晶体结构

  摘要：

  据报道，从2-甲基-6-（芳基/杂芳基）hexa-3,5-diyn-2合成了一系列末端芳基-和杂芳基-丁二炔（ArC⋮C-C⋮CH）4a - h。 -ol前体。溶液中4a - h的稳定性取决于浓度：许多衍生物可以稀溶液形式保存几天甚至几周。已经获得了五种ArC⋮C-C⋮CH衍生物的X射线晶体结构[Ar = 2-（9-芴基），4-联苯，2-吡啶基，4-吡啶基和2-吡唑基]。

  DOI：

  10.1021/jo0615697

文献信息

• General Method for the Preparation of Alkyne-Functionalized Oligopyridine Building Blocks
  作者：Raymond Ziessel、Jean Suffert、Marie-Thérèse Youinou

  DOI：10.1021/jo960538g

  日期：1996.1.1

  diynes provides access to ditopic bipyridine or terpyridine ligands oligoPy(C&tbd1;C)(4)oligoPy comprising a tetrayne spacer. Quantitative formation of air-stable copper(I) complexes is described for the 6,6'-substituted ligands. A single crystal X-ray structure of complex 22a shows that the two ligands are interlocked around the copper(I) center in a pseudotetrahedral arrangement, similar to the structure

  通过用含水甲醇碱处理从其形成末端二炔低聚（C＆tbd1; C）（2）H。oligoPy（C＆tbd1; C）（2）H与BrC＆tbd1; CSiEt（3）的反应产生了甲硅烷基化的三炔oligoPy（C＆tbd1; C）（3）SiEt（3）。进一步的同源性受到炔丙基链C-2碳上正丙胺的亲核攻击的限制，产生顺式/顺式（48％），顺式/反式（33％）和反式/反式（19 ％）烯胺二炔化合物21a-c。末端二炔的Glaser氧化自偶联提供了对包含四炔间隔基的二位联吡啶或三联吡啶配体oligoPy（C＆tbd1; C）（4）oligoPy的访问。描述了6,6'-取代的配体的空气稳定铜（I）配合物的定量形成。配合物22a的单晶X射线结构表明，两个配体以伪四面体排列互锁在铜（I）中心周围，类似于从NMR和FAB（+）数据推导的结构。本文报道的合成方法代表了大规模制备炔基官能化的低聚吡啶的有价值的方法。
• Stepwise construction of polyalkyne modules grafted on oligopyridine synthons
  作者：Raymond Ziessel、Jean Suffert

  DOI：10.1016/0040-4039(96)00210-9

  日期：1996.3

  We report on the stepwise homologation of the ethynyl substituted pyridine, 2,2′-bipyridine, and 2,2′:6′,6″-terpyridine with bromoethynyl(triethyl)silane using the Chodkiewicz method. Chelating ligands bearing one or two triethylsilylbutadiyne, one or two triethylsilylhexatriyne subunits have been synthesized and fully characterized.

  我们报道了使用Chodkiewicz方法将乙炔基取代的吡啶，2,2'-联吡啶和2,2'：6'，6''-吡啶与溴乙炔基（三乙基）硅烷逐步同系化。已经合成并充分表征了带有一个或两个三乙基甲硅烷基丁二炔，一个或两个三乙基甲硅烷基己三炔亚基的螯合配体。
• Unusual Attractive Au–π Interactions in Small Diacetylene‐Modified Gold Clusters
  作者：Mitsuhiro Iwasaki、Yukatsu Shichibu、Katsuaki Konishi

  DOI：10.1002/anie.201814359

  日期：2019.2.18

  attractive Au–π interactions in diacetylene‐modified [core+exo]‐type [Au8]4+ clusters. The 4‐phenyl‐1,3‐butadiynyl‐modified cluster has unusually short Au–Cα distances in the crystal structure, revealing the presence of attractive interactions between the coordinating C≡C moieties and the neighboring bitetrahedral Au6 core, which is further supported by IR and NMR spectra. Such weak interactions are not

  众所周知，炔烃在与金属形成络合物时起π-酸的作用。我们在联乙炔改性的[core + exo ]型[Au 8 ] 4+簇中发现了前所未有的有吸引力的Au-π相互作用。的4-苯基1,3-丁二改性簇具有不寻常的短的Au-C α的晶体结构的距离，揭示有吸引力相互作用的协调C≡C部分和相邻的Au bitetrahedral之间存在6核，进一步由IR和NMR光谱支持。在单乙炔修饰的簇中未发现这种弱相互作用，这表明它们对二乙炔配体具有特异性。有吸引力的Au-π相互作用可能与二炔部分中π*轨道的低能量有关，金核的价电子可以返还给它。[Au 8 ] 4+团簇在紫外/可见光吸收带中相对于相应的单炔类团簇显示出大于10 nm的明显红移，这表明Au-π相互作用具有明显的电子扰动效应。
• Are Terminal Aryl Butadiynes Stable? Synthesis and X-ray Crystal Structures of a Series of Aryl- and Heteroaryl-butadiynes (Ar−C⋮C−C⋮C−H)
  作者：Kara West、Changsheng Wang、Andrei S. Batsanov、Martin R. Bryce

  DOI：10.1021/jo0615697

  日期：2006.10.1

  The synthesis and isolation are reported of a range of terminal aryl- and heteroaryl-butadiynes (ArC⋮C−C⋮CH) 4a−h from 2-methyl-6-(aryl/heteroaryl)hexa-3,5-diyn-2-ol precursors. The stability of 4a−h in solution is concentration dependent: many of the derivatives can be stored as dilute solutions for several days or even weeks. The X-ray crystal structures have been obtained for five ArC⋮C−C⋮CH derivatives

  据报道，从2-甲基-6-（芳基/杂芳基）hexa-3,5-diyn-2合成了一系列末端芳基-和杂芳基-丁二炔（ArC⋮C-C⋮CH）4a - h。 -ol前体。溶液中4a - h的稳定性取决于浓度：许多衍生物可以稀溶液形式保存几天甚至几周。已经获得了五种ArC⋮C-C⋮CH衍生物的X射线晶体结构[Ar = 2-（9-芴基），4-联苯，2-吡啶基，4-吡啶基和2-吡唑基]。
• Oligoyne Single Molecule Wires
  作者：Changsheng Wang、Andrei S. Batsanov、Martin R. Bryce、Santiago Martín、Richard J. Nichols、Simon J. Higgins、Víctor M. García-Suárez、Colin J. Lambert

  DOI：10.1021/ja9061129

  日期：2009.11.4

  We report the electrical conductance at the single molecule level of the oligoyne molecular wires Py-(C C)(n)-Py (n = 1, 2 and 4; Py = 4-pyridyl) using STM-molecular break junction techniques in Au vertical bar molecule vertical bar Au configurations. The conductance histograms reveal multiple series of peaks attributed to differing contact geometries between the pyridyl head groups and the gold electrodes. Both experimental and theoretical evidence point to the higher conduction groups being related to adsorption of the pyridyl group at more highly coordinated sites such as step edges or alongside gold adatoms. All three conduction groups in the oligoyne series show a remarkably low beta value of (0.06 +/- 0.03) angstrom(-1), that is, the conductance is almost independent of molecular length. 4,4'-Bipyridyl studied under the same conditions does not follow this exponential decay series. Theoretical calculations using a combination of density functional theory and nonequilibrium Green's function formalism support the experimental results. We conclude that oligoynes and polyynes are a very promising class of molecular wires for integration into electronic circuitry.