2,3-bis((trimethylsilyl)ethynyl)pyridine | 216979-80-5

• 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: 2,3-bis((trimethylsilyl)ethynyl)pyridine
• 英文别名: Trimethyl-[2-[2-(2-trimethylsilylethynyl)pyridin-3-yl]ethynyl]silane
• CAS: 216979-80-5
• 化学式: C₁₅H₂₁NSi₂
• 分子量: 271.509
• InChiKey: LKHHBXWWZBWBGL-UHFFFAOYSA-N

物化性质

• 沸点：
  312.4±42.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.54
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  2,3-bis((trimethylsilyl)ethynyl)pyridine 在 titanium(IV) isopropylate 、 异丙基氯化镁 作用下， 以 乙醚 为溶剂， 反应 2.5h， 以84%的产率得到(Z)-2-[2-(trimethylsilyl)ethenyl]-3-[(trimethylsilyl)ethynyl]pyridine
  参考文献：
  名称：

  Site-Selective Monotitanation of Dialkynylpyridines and Its Application for Preparation of Highly Fluorescent π-Conjugated Oligomers

  摘要：

  Reaction of Ti(O-i-Pr)(4)/2i-PrMgCl reagent with 2,n-bis[(trimethylsilyl)ethynyl]pyridines, where n is 3, 4, 5, and 6, or with 3,4-bis[(trimethylsilyl)ethynyl]pyridines, proceeded with excellent site-selectivity to afford the corresponding monotitanated complex. Synthetic application of the reaction was demonstrated by an efficient preparation of pi-conjugated oligomers having pyridine and enyne units alternately, which possess intense blue fluorescence emission.

  DOI：

  10.1021/ol048316p
• 作为产物：
  描述：

  2-溴-3-羟基吡啶 在 四(三苯基膦)钯 三乙胺 、 二异丙胺 作用下， 以 二氯甲烷 为溶剂， 反应 13.0h， 生成 2,3-bis((trimethylsilyl)ethynyl)pyridine
  参考文献：
  名称：

  Rapid Bergman Cyclization of 1,2-Diethynylheteroarenes

  摘要：

  The synthesis and cyclization of acyclic quinoxaline, pyridine, and pyrimidine enediynes (1-3) are described. These compounds were prepared using palladium(0) coupling of trimethylsilyl acetylene to o-dihalo- or o-halotriflic heteroarenes. All compounds were prepared in modest to good yields. The enediynes prepared were shown to undergo Bergman cyclization. Kinetics over a minimum of 3 half-lives were used to construct Arrhenius plots. Pyrimidine 3 was found to have an activation energy of 16.1 kcal/mol. Cyclization of the closest known aromatic analogue, o-diethynylbenzene (15), has E-a = 25.1 kcal/mol (Grissom, J. W.; Calkins, T. L.;McMillen, H. A.; Jiang, Y. J. Org. Chem. 1994, 59, 5833-5835). Pyridine 2 and quinoxaline 1 gave activation energies of 21.5 and 33.6 kcal/mol, respectively. The results illustrate that heteroarenes can be used to activate Bergman cyclization. We expect these compounds to play an important role in furthering the understanding of Bergman cyclization and in aiding the development of new biologically significant enediynes.

  DOI：

  10.1021/jo980879p

文献信息

• Triplet Acetylenes as Synthetic Equivalents of 1,2-Bicarbenes:  Phantom n,π* State Controls Reactivity in Triplet Photocycloaddition
  作者：Tarek A. Zeidan、Serguei V. Kovalenko、Mariappan Manoharan、Ronald J. Clark、Ion Ghiviriga、Igor V. Alabugin

  DOI：10.1021/ja043803l

  日期：2005.3.1

  reactive triplet excited states (intersystem crossing: ISC) and/or to the radical-anion (photoelectron transfer from the diene to the excited acetylene: PET). Dramatically enhanced ISC between pi-pi S(1) state and "phantom" n,pi triplet excited state is likely to be important in directing reactivity to the triplet pathway. The role of PET can be minimized by the judicious choice of reaction conditions

  二芳基乙炔，其中芳基之一是吡啶或吡嗪，经过有效的三线态光环加成反应生成 1,4-环己二烯，形成 1,5-二芳基取代的四环 [3.3.0.0(2,8).0。 (4,6)]辛烷（同四环烷）。在吡嗪基乙炔的情况下，主要的同四环烷产物经历二次光化学重排，导致二芳基取代的三环 [3.2.1.0(4,6)] oct-2-烯。机械和光物理研究表明，光环加成通过亲电子三重激发态进行，而随后重排为三环辛烯则通过单重激发态进行。环加成的化学和量子产率通常与芳基取代基的电子受体特征相关，但会因光物理因素而减弱，例如乙炔单重激发态转化为反应性三重激发态（系统间交叉：ISC）和/或自由基阴离子（光电子从二烯转移到激发态乙炔：PET）之间的竞争。pi-pi S(1) 状态和“幻影”n、pi 三重态激发态之间显着增强的 ISC 可能在将反应性导向三重态通路方面很重要。PET 的作用可以通过明智地选择反应条件（溶剂、浓度
• Benzannulation of Heterocyclic Frameworks by 1,1-Carboboration Pathways
  作者：René Liedtke、Fabian Tenberge、Constantin G. Daniliuc、Gerald Kehr、Gerhard Erker

  DOI：10.1021/jo502753s

  日期：2015.2.20

  A small series of S- and N-heterocyclic 1,2-bis(trimethylsilylethynyl)arenes (2, 9, and 12) react with the strongly electrophilic borane B(C6F5)3 in consecutive 1,1-carboboration sequences to benzannulated heterocyclic systems. With this approach, highly substituted carbazole (6), benzothiophene (10), and quinoline (14) derivatives can be synthesized. While benzannulation occurs in all three cases

  一小系列S-和N-杂环1,2-双（三甲基硅乙炔）芳烃（的2，9，和12）与强电硼烷B（C反应6 ˚F 5）3在连续的1,1- carboboration序列苯环杂环系统。通过这种方法，可以合成高度取代的咔唑（6），苯并噻吩（10）和喹啉（14）衍生物。尽管在所有三种情况下均发生苯甲环化，但反应在细节上完全不同。最后，一锅式脱硼反应会生成羟基-戊烯，如羟基咔唑7所示和羟基-苯并噻吩11。
• The Cobalt-Way to Heterophenylenes: Syntheses of 2-Thianorbiphenylenes, Monoazabiphenylenes, and Linear 1-Aza[3]phenylene {Biphenyleno[2,3-a]cyclobuta[1,2-b]pyridine}
  作者：K. Vollhardt、Verena Engelhardt、J. Garcia、Aude Hubaud、Konstantin Lyssenko、Spyros Spyroudis、Tatiana Timofeeva、Paul Tongwa

  DOI：10.1055/s-0030-1259087

  日期：2011.1

  CpCo(CO) 2 catalyzes the cocyclization of ortho-diethynylthiophenes and -pyridines with alkynes to construct the corresponding thia- and azaphenylenes. This strategy is applied to the synthesis of linear 1-aza[3]phenylene, the first higher heterophenylene.

  CpCo(CO) 2 催化邻二乙炔噻吩和吡啶与炔烃的共环化，以构建相应的硫杂苯和氮杂苯。该策略用于合成线性1-氮杂[3]亚苯基，这是第一个高级杂亚苯基。
• Alternative approaches to (Z)-1,2-bis(2-bromopyridin-3-yl)ethenes, key intermediates in the synthesis of the 1,10-phenanthroline core
  作者：Giorgio Chelucci、Salvatore Baldino、Gerard A. Pinna、Barbara Sechi

  DOI：10.1016/j.tetlet.2008.02.112

  日期：2008.4

  A study on the synthesis of (Z)-1,2-bis(2-bromopyridin-3-yl)ethenes, key intermediates in the preparation of 1,10-phenanthrolines, based on selective Sonogashira and Suzuki-Miyaura cross-coupling reactions has been carried out. (C) 2008 Elsevier Ltd. All rights reserved.
• Rapid Bergman Cyclization of 1,2-Diethynylheteroarenes
  作者：Chang-Sik Kim、K. C. Russell

  DOI：10.1021/jo980879p

  日期：1998.11.1

  The synthesis and cyclization of acyclic quinoxaline, pyridine, and pyrimidine enediynes (1-3) are described. These compounds were prepared using palladium(0) coupling of trimethylsilyl acetylene to o-dihalo- or o-halotriflic heteroarenes. All compounds were prepared in modest to good yields. The enediynes prepared were shown to undergo Bergman cyclization. Kinetics over a minimum of 3 half-lives were used to construct Arrhenius plots. Pyrimidine 3 was found to have an activation energy of 16.1 kcal/mol. Cyclization of the closest known aromatic analogue, o-diethynylbenzene (15), has E-a = 25.1 kcal/mol (Grissom, J. W.; Calkins, T. L.;McMillen, H. A.; Jiang, Y. J. Org. Chem. 1994, 59, 5833-5835). Pyridine 2 and quinoxaline 1 gave activation energies of 21.5 and 33.6 kcal/mol, respectively. The results illustrate that heteroarenes can be used to activate Bergman cyclization. We expect these compounds to play an important role in furthering the understanding of Bergman cyclization and in aiding the development of new biologically significant enediynes.