bis(p-tolylethynyl)dimethylsilane

• 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: bis(p-tolylethynyl)dimethylsilane
• 英文别名: Bis[(4-methylphenyl)ethynyl]dimethylsilane；dimethyl-bis[2-(4-methylphenyl)ethynyl]silane
• 化学式: C₂₀H₂₀Si
• 分子量: 288.464
• InChiKey: RCJCQWICJOMSFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.49
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 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：

  bis(p-tolylethynyl)dimethylsilane 在 盐酸 、 Cp₂ZrEt₂ 、 水 、 copper(l) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 trans,trans-1,4-bis(4-methylphenyl)-1,3-butadiene
  参考文献：
  名称：

  锆介导的双(炔基)硅烷的两个炔基的分子内碳-碳键形成

  摘要：

  用 Cp2ZrEt2 (1)（Cp = 环戊二烯基）和 H2O/CuCl 依次处理双（苯基乙炔基）硅烷 (PhC⋮C)2SiR2（R = Me (2a)、Et (2b) 或 Ph (2c)）得到（ 1E,3E)-1,4-二苯基-1,3-丁二烯 (3) 水解后的产率为 56-88%。另一方面，2a-h 与 Cp2ZrEt2 的反应混合物的水解以 61-87% 的产率得到硅杂环丁烯衍生物 4a-h。当 t-BuC5H4 用作锆茂衍生物的配体时，含锆中间体 7 作为适合 X 射线分析的晶体获得。7的结构表明中间体含有锆杂环丁烯-硅杂环丁烯稠环系统。硅杂环丁烯 4a 与 CuCl 的反应选择性地打开了硅杂环丁烯环。在催化量的 Pd(PPh3)4 存在下用 PhI 进一步处理反应混合物，得到 1,3,4-三苯基-1-甲硅烷基-1，3-丁二烯化合物16。在α-位具有炔基甲硅烷基的锆环戊二烯以82-98%的产率提供锆环己二烯衍生物19。什

  DOI：

  10.1021/ja972381v

文献信息

• Zirconium- and Silicon-Containing Intermediates with Three Fused Rings in a Zirconocene-Mediated Intermolecular Coupling Reaction
  作者：Wen-Xiong Zhang、Shaoguang Zhang、Xiaohua Sun、Masayoshi Nishiura、Zhaomin Hou、Zhenfeng Xi

  DOI：10.1002/anie.200903329

  日期：2009.9.14

  Veritable Jack‐in‐the‐box: The isolation and characterization of key Zr/Si‐containing intermediates was achieved for a zirconocene‐mediated intermolecular coupling reaction (see scheme). The fate of the various functional groups was determined, and the reactivity of intermediate 1 with a variety of unsaturated substrates was also investigated.

  名副其实的杰克：锆茂介导的分子间偶联反应（参见方案）实现了关键含Zr / Si中间体的分离和表征。确定了各种官能团的命运，并且还研究了中间体1与各种不饱和底物的反应性。
• Efficient One-Pot Synthesis of N-Containing Heterocycles by Multicomponent Coupling of Silicon-Tethered Diynes, Nitriles, and Isocyanides through Intramolecular Cyclization of IminoacylZr Intermediates
  作者：Shaoguang Zhang、Wen-Xiong Zhang、Zhenfeng Xi

  DOI：10.1002/chem.201000708

  日期：——

  intermediates underwent intramolecular cyclization to afford tetrasubstituted 5‐azaindoles, whereas intramolecular cyclization of bis(iminoacyl)Zr intermediates led to the formation of dihydropyrrolo[3,2‐c]azepines. The structure of a bis(iminoacyl)Zr intermediate, formed through insertion of two molecules of CyNC into the ZrC bond, and structures of two dihydropyrrolo[3,2‐c]azepines were characterized

  锆茂系介导的硅链二炔，腈和异氰化物的偶氮锆偶联可实现5-氮杂吲哚和二氢吡咯并[3,2- c ]氮杂的高效多组分合成。的合成，结构，和单-和二（亚氨基）的分子内环化 Zr的中间体进行了研究，以阐明该反应过程。在水解后，分离的单（亚氨基）锆中间体后行分子内环化，得到四取代5-氮杂吲哚，而双分子内环化（亚氨基）锆中间体导致形成的二氢吡咯并[3,2- Ç ]吖庚因。双（亚氨基酰基）的结构Zr的中间，通过CYNC的两个分子的插入形成为Zr的 C键，以及两个二氢的结构并[3,2- c ^ ]吖庚因的特点是单晶X射线结构分析。
• One-Pot Multicomponent Synthesis of Azaindoles and Pyrroles from One Molecule of a Silicon-Tethered Diyne and Three or Two Molecules of Organonitriles Mediated by Zirconocene
  作者：Shaoguang Zhang、Xiaohua Sun、Wen-Xiong Zhang、Zhenfeng Xi

  DOI：10.1002/chem.200902411

  日期：2009.11.23

  A zirconocene‐mediated one‐pot multicomponent synthesis process leading to the synthesis of pyrrolo[3,2‐c]pyridine (5‐azaindoles) and pyrrole derivatives has been developed starting from a silicon‐tethered diyne and three or two different or identical organonitriles. Pyrrolo[3,2‐c]pyridine and pyrrole derivatives with diverse structures and substitution patterns have been highly selectively prepared

  锆茂茂介导的单锅多组分合成工艺从硅系二炔和三个或两个不同或相同的有机腈开始，导致合成吡咯并[3,2- c ]吡啶（5-氮杂吲哚）和吡咯衍生物。 。通过该方案高度选择性地制备了具有不同结构和取代方式的吡咯并[3,2- c ]吡啶和吡咯衍生物。各种各样的具有吸电子和供电子基团的脂肪族或芳香族有机腈和硅系二炔被用来以良好的优异分离产率提供5-氮杂吲哚和/或吡咯。在Cp 2 Zr II介导的一个（PhC≡C）反应中形成的关键中间体2 SiMe 2中，通过X射线单晶结构分析表征了i PrCN和一个p- tolylCN的两个分子，这使我们对反应过程有了很好的了解。
• Cleavage and Reorganization of Zr−C/Si−C Bonds Leading to Zr/Si−N Organometallic and Heterocyclic Compounds
  作者：Shaoguang Zhang、Wen-Xiong Zhang、Jing Zhao、Zhenfeng Xi

  DOI：10.1021/ja1074932

  日期：2010.10.13

  The t-BuCN-stabilized zirconacyclopropene-azasilacyclopentadiene complexes 2 are generated in situ in high yields from the Si-tethered diynes, Cp2Zr(II) species, and 2 equiv of t-BuCN via a coordination-induced Zr-C/Si-C bond cleavage and reorganization. Complexes 2 have been demonstrated to be synthetically very useful. A variety of novel Zr/Si organo-bimetallic compounds and Si/N heterocyclic compounds, such as azasilacyclopentadienes, azasilacyclohexadienes, and allenylazazirconacycles, are obtained in high yields when complexes 2 are treated with ketones, carbodiimides, alkynes, elemental sulfur (S-8), acid chlorides, or nitriles. In this chemistry, t-BuCN behaves as both an initiator and a brake/release handle to initiate and control the reaction process.
• Zirconocene-Mediated Intermolecular Coupling of One Molecule of Si-Tethered Diyne with Three Molecules of Organonitriles:  One-Pot Formation of Pyrrolo[3,2-<i>c</i>]pyridine Derivatives via Cleavage of C⋮N Triple Bonds of Organonitriles
  作者：Xiaohua Sun、Congyang Wang、Zhiping Li、Shiwei Zhang、Zhenfeng Xi

  DOI：10.1021/ja0497173

  日期：2004.6.1

  One Si-tethered diyne is coupled in one pot with three molecules of organonitriles promoted by a low-valent zirconocene species. Cleavage of one of the three CN triple bonds and cleavage of the two Si-C bonds take place to afford pyrrolo[3,2-c]pyridine derivatives after hydrolysis.