(1,1'-phenyl-1,1'-silacyclohex-1-yl)disiloxane | 18753-38-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1,1'-phenyl-1,1'-silacyclohex-1-yl)disiloxane
• 英文别名: 1,1'-Oxybis(1-phenylsilacyclohexane)；1-phenyl-1-(1-phenylsilinan-1-yl)oxysilinane
• CAS: 18753-38-3
• 化学式: C₂₂H₃₀OSi₂
• 分子量: 366.651
• InChiKey: NTTNTGGNQYDXHZ-UHFFFAOYSA-N

物化性质

• 沸点：
  430.0±14.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.08
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  苯基三氯硅烷 在 magnesium 、 三乙胺 、 potassium hydroxide 作用下， 以 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 5.0h， 生成 (1,1'-phenyl-1,1'-silacyclohex-1-yl)disiloxane
  参考文献：
  名称：

  1-Phenyl-1-halo-1-silacyclohexanes

  摘要：

  The approaches to synthesis of 1-phenyl-1-halo-1-silacyclohexanes C5H10Si(Ph)X (X = F, Cl, Br) have been examined. 1-Phenyl-1-chloro-1-silacyclohexane has been prepared via the known reaction of phenyltrichlorosilane with dimagnesium derivative of 1,5-dibromopentane; up to 20% of 1-bromo-1-phenyl-1-silacyclohexane admixture is formed along with the target product. The minor product formation has been prevented using an alternative method of chlorination of 1-phenyl-1-silacyclohexane with N-chlorosuccinimide. 1-Phenyl-1-fluoro-1-silacyclohexane has been obtained in close to quantitative yield via the reaction of 1-phenyl-1-chloro-1-silacyclohexane with SbF3 and in 70% yield via its reaction with HF. The synthesis of 1-phenyl-1-bromo-1-silacyclohexane via bromination of 1-phenyl-1-chloro-1-silacyclohexane with N-bromosuccinimide has given the target product as a minor one, the major product being disiloxane formed due to hydrolysis of the Si-Br bond.

  DOI：

  10.1134/s1070363216080132

文献信息

• 1-t-Butyl-1-phenyl-1-silacyclohexane: Synthesis, conformational analysis in gas and solution by GED, FT-IR and theoretical calculations
  作者：Bagrat A. Shainyan、Elena N. Suslova、Tran Dinh Phien、Sergey A. Shlykov、Larisa P. Oznobikhina

  DOI：10.1016/j.jorganchem.2020.121433

  日期：2020.9

  t-Bu group, at silicon, was synthesized via the sequence of reactions PhSiCl3 → Ph(Cl)Si(CH2)5 → Ph(t-Bu)Si(CH2)5, and its molecular structure and conformational preferences were studied by gas-phase electron diffraction (GED), temperature variable IR spectroscopy and quantum chemical calculations of the isolated conformers and their solvate complexes in gas and in polar medium. The predominance of the

  通过反应顺序PhSiCl 3 →Ph（Cl）Si（CH）合成了1-叔丁基-1-苯基-1-硅环己烷1（在硅上具有最大取代基的第一个双取代硅杂环己烷t- Bu基）。2）5 →Ph（t- Bu）Si（CH 2）5，通过气相电子衍射（GED），温度可变红外光谱和分离的构象异构体及其分子的量子化学计算，研究了其分子结构和构象偏好。在气体和极性介质中的溶剂合物。气相中t -Bu eq构象异构体的优势（由GED确定的1- Ph ax：1- Ph eq  = 92：8，ΔG °= 1.63 kcal / mol与在DFT和MP2理论水平上的量子化学计算结果一致。
• Very low-temperature dynamic ²⁹ Si NMR study of the conformational equilibrium of (1,1′-phenyl-1,1′-silacyclohex-1-yl)disiloxane
  作者：Erich Kleinpeter、Bagrat A. Shainyan

  DOI：10.1002/mrc.4870

  日期：2019.6

  from 140 to 90 K. Most commonly used nuclei for conformational analysis by NMR spectroscopy are H, C, and often F (in organofluorine compounds) nuclei. To the best of our knowledge, there are no examples of the use of Si NMR spectroscopy at low temperature for the conformational analysis of silacyclohexanes and, more generally, of any conformationally flexible organosilicon molecules. In continuation

  低温溶液核磁共振光谱是硅杂环己烷构象分析最有启发性的方法。鉴于与环己烷相比，硅杂环己烷具有更高的灵活性（由于延长的 C─Si 键和扩大的 C─Si─C 角），环互变过程中适当 NMR 信号的脱聚温度要低得多，并且在范围从 140 到 90 K。通过 NMR 光谱法进行构象分析最常用的核是 H、C，通常是 F（在有机氟化合物中）核。据我们所知，目前还没有在低温下使用 Si NMR 光谱对硅环己烷进行构象分析的例子，更一般地说，还没有对任何构象柔性有机硅分子进行构象分析的例子。为了继续对硅杂环己烷和硅杂（杂）环己烷的构象分析进行研究，我们合成了（1,1'-苯基-1,1'-硅杂环己-1-基）二硅氧烷 1 并检查了其低温 H 和C核磁共振谱；不幸的是，就化合物 1 的构象组成而言，两者都没有提供信息。因此，我们在理论的 M062X/6-311G(d,p) 和 MP2/6-311G(d,p) 水平理论上估计了三种可能的构象异构体（图
• 1-Phenyl-1-X-1-silacyclohexanes (X = MeO, OH, Me2N)
  作者：E. N. Suslova、B. A. Shainyan

  DOI：10.1134/s1070363217070349

  日期：2017.7

  By the reaction of nucleophilic substitution of chlorine in 1-phenyl-1-chloro-1-silacyclohexane new 1-phenyl-1-X-1-silacyclohexanes (D = DeD mu D, DDe, DeD mu N-2) have been synthesized and their stability with respect to the formation of (1,1'-phenyl-1,1'-silacyclohex-1-yl)disiloxane have been investigated.
• Conformational Analysis of (1,1′-Phenyl-1,1′-silacyclohex-1-yl)disiloxane. DFT and Low-Temperature 13C NMR Spectroscopy Study
  作者：B. A. Shainyan、E. Kleinpeter、E. N. Suslova

  DOI：10.1134/s1070363219040121

  日期：2019.4

  The DFT and MP2 theoretical conformational analysis of the recently synthesized (1,1-phenyl-1,1-silacyclohex-1-yl)disiloxane has revealed the energetic preference of the Ph-ax,Ph-ax conformer. The Ph-ax,Ph-ax: Ph-ax,Ph-eq: Ph-eq,Ph-eq conformers ratio has been estimated as of 46.6: 33.1: 20.3 from the M062X/6-311G(d,p) free energy simulation, suggesting the possibility of detecting individual conformers experimentally, e.g., by low-temperature H-1 and C-13 NMR spectroscopy. However, only the presence of several conformers has been detected by means of H-1 NMR spectroscopy at 113 K; determination of the (Hz) and G(#) (kcal/mol) parameters for the 6-membered ring interconversion has been impossible due to the signals broadening at low temperature, signal temperature shifts, and extremely low barrier of ring inversion at T-c < 113 K.
• Gilman; Gorsich, 1957, vol. 131176, p. 23,43
  作者：Gilman、Gorsich

  DOI：——

  日期：——