乙炔基(二甲基)硅烷 | 1777-04-4

• 分子结构分类: 有机化合物 - 乙炔化物 - 碳化物
• 中文名称: 乙炔基(二甲基)硅烷
• 英文名称: (dimethylsilyl)acetylene
• 英文别名: Dimethyl(ethinyl)silan；dimethylethynylsilane；Ethynyl(dimethyl)silane；ethynyl(dimethyl)silane
• CAS: 1777-04-4
• 化学式: C₄H₈Si
• 分子量: 84.193
• InChiKey: MAFZTCHQTVYQHJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.65
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  乙炔基(二甲基)硅烷 在 dihydrogen hexachloroplatinate 作用下， 以 四氢呋喃 为溶剂， 以2.8%的产率得到Si-dodecamethylcyclohexasilethene
  参考文献：
  名称：

  Cyclodimethylsilethenes (Me2SiCHCH)n

  摘要：

  Dodecamethylcyclohexasilethene (Me(2)SiCH=CH)(6) (1) was synthesized by autohydrosilylation of HMe(2)SiC=CH in a tetrahydrofuran solution in the presence of H2PtCl6 under high dilution. An analogous reaction of Me(2)Si(C=CH)(2) or E-HC=CMe(2)SiCH=CHSiMe(2)C=CH with E,E-Me(2)Si(CH=CHSiMe(2)H)2 gave octamethylcyclotetrasilethene (Me(2)SiCH=CH)(4) (2) and decamethylcyclopentasilethene (Me(2)SiCH=CH)(5) (3) respectively. The X-ray structure of 3 is presented.

  DOI：

  10.1016/0022-328x(95)05199-y
• 作为产物：
  描述：

  2,2-Dimethyl-2-sila-1,3-bis(diazo)propan 以 various solvent(s) 为溶剂， 生成 乙炔基(二甲基)硅烷
  参考文献：
  名称：

  Trommer, Martin; Sander, Wolfram; Marquard, Claudia, Angewandte Chemie, 1994, vol. 106, # 7, p. 816 - 818

  摘要：

  DOI：

文献信息

• Alkynylsilanes and Alkynyl(vinyl)silanes. Synthesis,Molecular Structures and Multinuclear Magnetic Resonance Study
  作者：Bernd Wrackmeyer、Stefan Bayer、Oleg L. Tok、Elena V. Klimkina、Wolfgang Milius、Rhett Kempe、Ezzat Khan

  DOI：10.1515/znb-2010-0609

  日期：2010.6.1

  Alkynylsilanes bearing one to four alkynyl groups at silicon, with organyl groups (Me, Ph, Vin), H, Cl at silicon, and with substituents H, ⁿBu, ^tBu, Ph, C₆H₄-4-Me, 3-thienyl, CH₂NMe₂ at the C≡C bond, were prepared, and their ¹³C and ²⁹Si NMR data are reported. The results of X-ray structure analyses of three representative derivatives [di(phenylethynyl)dimethylsilane, di(phenylethynyl) methyl(phenyl)silane, and tri(phenylethynyl)methylsilane] are presented. The chemistry of mono- and dialkynylsilanes was further developed to prepare compounds with alternating Si atoms and C≡C bonds, affording new dialkynylsilanes as well as numerous new vinylsilanes which have also been characterized by ¹³C and ²⁹Si NMR spectroscopy in solution. In the case of ethynyl(triphenylsilylethynyl) dimethylsilane, the molecular structure was determined by X-ray diffraction.

  带有硅原子上一个到四个炔基的炔基硅烷，以及硅原子上带有甲基、苯基、乙烯基、氢、氯的有机基团，以及炔键上带有H、正丁基、叔丁基、苯基、4-甲基苯基、3-噻吩基、CH2NMe2等取代基的炔基硅烷已经制备，并报告了它们的13C和29Si核磁共振数据。三个代表性衍生物[二(苯乙炔基)二甲基硅烷、二(苯乙炔基)甲基(苯基)硅烷和三(苯乙炔基)甲基硅烷]的X射线结构分析结果被呈现。单炔基硅烷和二炔基硅烷的化学性质进一步发展，以制备交替的硅原子和C≡C键的化合物，得到了新的二炔基硅烷以及许多新的乙烯基硅烷，这些化合物也通过溶液中的13C和29Si核磁共振光谱进行了表征。在乙炔基(三苯基硅炔基)二甲基硅烷的情况下，分子结构是通过X射线衍射确定的。
• Helicenes Built from Silacyclopentadienes via Ring‐by‐Ring Knitting of the Helical Framework
  作者：Oleg L. Tok、Kamil Lang、Aleš Růžička、Josef Cvačka

  DOI：10.1002/anie.201811140

  日期：2019.2.4

  we report the synthesis of a new family of the heterohelicenes consisting of fused silacyclopentadiene rings formed via a facile and novel process. The treatment of oligo(alkynilydenesilylene) precursors of type H2C=CH−(SiMe2−C≡C)n−R (n=3–7), bearing a vinyl group on the terminal silicon atom, with 9‐borabicyclononane leads first to 1,2‐hydroboration of the terminal double bond which then continues

  尽管开发了用于合成螺旋烯的协议，表面上存在明显的多样性，但它们基本上遵循相同的策略：在一个关键步骤中闭合一个或多个内部环。在本文中，我们报告了一个新的杂螺旋体家族的合成，该杂螺旋体由稠合的硅杂环戊二烯环组成，它们是通过一种简便而新颖的方法形成的。H 2 C = CH-（SiMe 2- C≡C）n -R（n= 3-7），在末端硅原子上带有乙烯基，带有9-borabicyclononane会首先导致末端双键的1,2-氢硼化，然后继续进行分子内1,1-碳硼化反应的级联，并伴随着在每个步骤之后，通过关闭新的硅环，可以使目标甲硅烷基苯环目前具有多达七个缩合的硅环，并具有极高的收率。根据XRD分析，七环化合物11b的七个稠合的甲硅烷基环形成几乎完整的螺旋线。提出的单反应顺序是从容易获得的线性前驱物开始逐个环环编织螺旋骨架的第一个示例。
• Kinetics and mechanisms of .alpha.- and .beta.-eliminations of alkoxysilanes from saturated and unsaturated carbon frameworks
  作者：Sukhamaya. Bain、Sina. Ijadi-Maghsoodi、Thomas J. Barton

  DOI：10.1021/ja00216a039

  日期：1988.4

  favorable elimination of Me/sub 3/SiOMe from Me/sub 3/SiSiMe/sub 2/CH/sub 2/OMe does not occur. From kinetic studies and trapping experiments, this is found to be due to a more favorable A-factor for three-centered elimination of :CH/sub 2/. Three-centered elimination of Me/sub 3/SiOMe from an sp/sup 2/-hybridized carbon to afford a vinylidene is found to be more facile than the analogous elimination from

  尽管 Me/sub 3/SiCH/sub 2/SiMe/sub 2/OMe 经历了 Me/sub 3/SiOMe 的热诱导 ..beta..-消除以提供二甲基硅烯，但 Me/sub 3/SiOMe 从热力学上有利地消除Me/sub 3/SiSiMe/sub 2/CH/sub 2/OMe 不会发生。从动力学研究和捕获实验中，发现这是由于对三中心消除 :CH/sub 2/ 更有利的 A 因子。发现从 sp/sup 2/-杂化碳中三中心消除 Me/sub 3/SiOMe 以提供亚乙烯基比从 sp/sup 3/-杂化碳中的类似消除更容易，因为两者都更有利活化能和 A 因子。因此，由于 ..cap alpha..-消除到 H/sub 2/C= 的更大便利性，不会发生从 H/sub 2/-C(OMe)SiMe/sub 2/SiMe/sub 3/ 形成硅丙二烯C：。
• Stepwise Reactions of Dimethylsilyl Acetylenes with Octacarbonyldicobalt
  作者：Sonae Kotani、Toshihiro Matsumoto、Hidemasa Yamaguchi、Kyo Shiina、Kenkichi Sonogashira

  DOI：10.1246/cl.1989.293

  日期：1989.2

  Treatment of bis(dimethylsilyl)acetylene 1 with more than two molar amount of octacarbonyldicobalt in cyclohexane gave the complex [(CO)4CoSiMe2C≡C–SiMe2Co(CO)4]Co2(CO)6, while treatment of 1 with one or 1.5 molar amount of octacarbonyldicobalt produced the complexes [HSiMe2C≡CSiMe2H]Co2(CO)6 and [HSiMe2C≡CSiMe2Co(CO)4]Co2(CO)6, respectively. The reactions of dimethyl(phenylethynyl)silane and its homologs with Co2(CO)8 were also investigated.

  用超过两摩尔量的八羰基二钴在环己烷中处理双(二甲基硅基)乙炔1，生成了复合物[(CO)4CoSiMe2C≡C–SiMe2Co(CO)4]Co2(CO)6，而用一摩尔或1.5摩尔量的八羰基二钴处理1，分别生成复合物[HSiMe2C≡CSiMe2H]Co2(CO)6和[HSiMe2C≡CSiMe2Co(CO)4]Co2(CO)6。还研究了二甲基(苯乙炔基)硅烷及其同类物与Co2(CO)8的反应。
• 1,1-Ethylboration Of Di(alkyn-1-yl)Silanes With Two And Three Si-H Functions. New Silacyclopentadienes
  作者：Bernd Wrackmeyer、Oleg L. Tok、Azim Khan、Amin Badshah

  DOI：10.1515/znb-2005-0303

  日期：2005.3.1

  The reaction of the di(alkyn-1-yl)silanes Me₂Si(C≡CSiMe₂H)₂ 1a and Me(H)Si(C≡CSiMe₂H)₂ 1b with triethylborane was studied. In the case of 1a, the 4-ethyl-3-diethylboryl-1,1-dimethyl-2,5- bis(dimethylsilyl)-1-sila-2,4-cyclop entadiene 2a was the sole product. In the case of 1b, the analogous silole 2b was formed along with two other products which were identified as di(alkenyl)silanes 3b and 4b, in which different types of electron-deficient Si-H-B bridges could be detected. All products were characterised by consistent sets of solution NMR data (¹H, ¹¹B, ¹³C and ²⁹Si NMR). The coupling constants ¹J(¹³C,¹³C) were measured for 2a and calculated by using DFT methods (B3LYP/6-311+G(d,p) level of theory)

  二(炔基-1-基)硅烷Me₂Si(C≡CSiMe₂H)₂ 1a和Me(H)Si(C≡CSiMe₂H)₂ 1b与三乙基硼的反应进行了研究。在1a的情况下，唯一的产物是4-乙基-3-二乙基硼基-1,1-二甲基-2,5-双(二甲基硅基)-1-硅-2,4-环戊二烯2a。在1b的情况下，类似的硅烯2b形成，还有两种其他产物，被鉴定为二(烯基)硅烷3b和4b，其中可以检测到不同类型的电子亏缺的Si-H-B桥。所有产物都通过一致的溶液NMR数据（¹H，¹¹B，¹³C和²⁹Si NMR）进行了表征。对于2a，测得了耦合常数¹J(¹³C,¹³C)，并通过使用DFT方法（B3LYP/6-311+G(d,p)理论水平）进行了计算。