((3-ethynylphenyl)ethynyl)trimethylsilane | 38170-79-5

• 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: ((3-ethynylphenyl)ethynyl)trimethylsilane
• 英文别名: 2-(3-Ethynylphenyl)ethynyl-trimethylsilane
• CAS: 38170-79-5
• 化学式: C₁₃H₁₄Si
• 分子量: 198.34
• InChiKey: PCHHDKZWEOPUFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 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-ethynylphenyl)ethynyl)trimethylsilane 在 1,3-双[(三甲基硅甲基)乙炔基]苯 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 四丁基氟化铵 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 12.5h， 生成 ethyl 3,5-bis[2-(3-ethynylphenyl)ethynyl]benzoate
  参考文献：
  名称：

  Solid-phase approaches toward cyclic oligomers

  摘要：

  Strategies were sought to effect cyclizations of oligo(m-phenylene ethynylene) by exploiting pseudo-high dilution effects on polymer supports. Using Pd/Cu-catalyzed coupling protocols, Merrifield's resin (1% crosslinked chloromethylated polystyrene) proved inadequate for site isolation; inter-site couplings ensued on the flexible support. Conversely, use of the Argopore resin, a more highly crosslinked polystyrene, inhibited inter-site interactions, and no identifiable final product could be separated from the resin. Spectroscopic and mass spectrometric methods indicated that the product from the Argopore resin might be a threaded catenane. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00930-9
• 作为产物：
  描述：

  1,3-双[(三甲基硅甲基)乙炔基]苯 在 甲醇 、 氢氧化钾 作用下， 以60%的产率得到((3-ethynylphenyl)ethynyl)trimethylsilane
  参考文献：
  名称：

  First Dewar benzene approach to acetylenic oligophenylene macrocycles: synthesis and structure of a molecular rectangle bearing two spindles

  摘要：

  一种新颖的杜瓦苯方法用于构建寡苯基大环，该方法通过引入杜瓦苯 1 作为构建模块，并应用于分子矩形 8 的合成，其结构通过晶体学方法进行了表征。

  DOI：

  10.1039/a908711g

文献信息

• One-Pot Transformation of Me₃Si-/Ph₂P(O)-Protected Ethynes to Unsymmetrical Arylethynes
  作者：Li-fen Peng、Jia-ying Lei、Li Wu、Zi-long Tang、Zhi-peng Luo、Yin-chun Jiao、Xin-hua Xu

  DOI：10.3184/174751918x15269925671284

  日期：2018.6

  Me₃Si-/Ph₂P(O)-protected ethynes were successfully transformed to unsymmetrical arylethynes via a one-pot Ph₂P(O)-deprotection/ [Pd(dppf)Cl₂]-catalysed coupling and one-pot Me₃Si-deprotection/Sonogashira coupling under mild conditions and in high yield. Unsymmetrical phenylethynes, unsymmetrical extended phenylene ethynylenes and unsymmetrical anthrylethynes were successfully synthesised in good to excellent yields.

  在温和的条件下，通过一锅 Ph2P(O)-脱保护/[Pd(dppf)Cl2]-催化偶联和一锅 Me3Si-Deprotection/Sonogashira 偶联，成功地将 Me3Si-/Ph2P(O)-protected ethynes 转化为非对称的芳炔类化合物，而且收率很高。成功合成了非对称苯乙炔、非对称扩展苯乙炔和非对称蒽乙炔，产率从良好到极佳。
• Oligosaccharide Analogues of Polysaccharides. Part 3. A new protecting group for alkynes: Orthogonally protected dialkynes
  作者：Chengzhi Cai、Andrea Vasella

  DOI：10.1002/hlca.19950780319

  日期：1995.5.10

  hydroxysulfide 16 with 15. The OH group of 27 was protected to yield the [dimethyl(oxy)propyl]dimethylsilyl}acetylenes (DOPSA's) 21, 28, and 29. The orthogonally protected acetylenes 20–22, 28, and 29 were de-trimethylsilylated to the new monoprotected acetylene synthons 30–34. The scope of the orthogonal protection was checked by regioselective deprotection of the dialkynes 39–42 (Scheme 4), prepared by alkylation

  通过在质子溶剂中（4）用碱处理，或在暴露OH基团之后，在质子惰性溶剂中用催化量的碱（5和8）处理3型二元炔（方案1）的区域选择性脱保护。在ME 3的Si-保护12（方案2）是惰性的催化丁基锂/ THF其转化11到9，而ķ 2 CO 3 / MeOH中转化的两个10到9，和12到13，表明需要更受阻的（羟丙基）甲硅烷基取代基。17–19（方案3）中的碳负离子的C-甲硅烷基化反应生成15的碳负离子导致20-22，但以合理的收率仅获得22。因此，关键中间体27是通过逆布鲁克重排23制备的，该逆向布鲁克重排是通过将羟基硫化物16与15进行甲硅烷基化而制得的。OH基团的27是受保护的，得到[ d imethyl（氧）p丙基]二甲基甲硅烷}乙炔（DOPSA的）21，28和29。正交保护的乙炔20–22、28和29被去三甲基甲硅烷基化为新的单保护的乙炔合成子30–34。正交的保护范围是由dialkyn
• Novel platinum–acetylide metallocycles constructed via a stepwise fragment coupling approach and their aggregation behaviour
  作者：Zhong-Yu Li、Lin Xu、Cui-Hong Wang、Xiao-Li Zhao、Hai-Bo Yang

  DOI：10.1039/c3cc42403k

  日期：——

  Through a stepwise fragment coupling approach, a family of novel platinum-acetylide metallocycles with well-defined shape and size were successfully constructed. Their aggregation behavior was investigated.

  通过逐步的片段偶联方法，成功地构建了具有明确定义的形状和尺寸的新型铂-乙炔金属环族。研究了它们的聚集行为。
• Extremely Long Lived Localized Singlet Diradicals in a Macrocyclic Structure: A Case Study on the Stretch Effect
  作者：Yuta Harada、Zhe Wang、Shunsuke Kumashiro、Sayaka Hatano、Manabu Abe

  DOI：10.1002/chem.201803076

  日期：2018.10.1

  σ‐bonded compound. Notably, the lifetime of this diradical (14 μs) is two orders of magnitude longer than that of a standard singlet diradical without a macrocyclic structure (≈0.2 μs) at 293 K. The species is persistent below a temperature of 100 K. In addition to the kinetic stabilization of the singlet diradical, the spontaneous oxidation of its corresponding ring‐closed compound at 298 K produced oxygenated

  局部单线双基自由基不仅在键-热解化学领域，而且在非线性光学材料领域都引起了广泛的关注。在这项研究中，通过使用新的分子设计策略获得了寿命极长的局部单线双基自由基，该策略通过大环增加了相应σ键合化合物的分子应变，从而使其动力学稳定。值得注意的是，在293 K下，该双自由基的寿命（14μs）比没有大环结构的标准单线双自由基（≈0.2μs）的寿命长两个数量级。该物种在100 K的温度下仍具有持久性。对于单线双自由基的动力学稳定性，其相应的闭环化合物在298 K下的自发氧化在大气条件下产生了氧化产物。显然，
• Synthesis and Structure of A Triptycene-Based Nanosized Molecular Cage
  作者：Chun Zhang、Chuan-Feng Chen

  DOI：10.1021/jo7017526

  日期：2007.11.1

  A triptycene-based nanosized molecular cage was designed and efficiently synthesized by Eglington−Glaser coupling reaction, and its structure was determined by NMR, MS spectrometry and X-ray analysis. Moreover, it was found that the cage molecules could pack into a microporous structure in the solid state and 1,3,5-trimethylbenzene molecules were located in the channels.

  设计并通过Eglington-Glaser偶联反应有效地合成了基于三萜的纳米分子笼，并通过NMR，MS光谱和X射线分析确定了其结构。此外，发现笼状分子可以堆积成固态的微孔结构，并且1,3,5-三甲基苯分子位于通道中。