1,1-diethynyl-1-silacyclohexane | 453568-99-5

• 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-diethynyl-1-silacyclohexane
• 英文别名: 1,1-diethynylsilacyclohexane；1,1-diethynylsilinane
• CAS: 453568-99-5
• 化学式: C₉H₁₂Si
• 分子量: 148.28
• InChiKey: HTYRAJOSDABKMQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.96
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  1,1-diethynyl-1-silacyclohexane 、 bis[(trimethylsilyl)ethynyl]fluoro(methyl)silane 在 溴化乙啶 、 magnesium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 0.5h， 以45%的产率得到1,1-bis[methylbis(trimethylsilylethynyl)silylethynyl]silacyclohexane
  参考文献：
  名称：

  New polyunsaturated organosilicon dendrimers based on 1,1-diethynyl-and 1-vinyl-1-ethynylsilacycloalkanes

  摘要：

  1,1-Dichloro- and 1-vinyl-1-chlorosilacyclanes were prepared by reactions of tetrachlorosilane or vinyltrichlorosilane with magnesium and 1,4-dibromobutane or 1,5-dibromopentane. The reactions of the products obtained with ethynylmagnesium bromide or bis(bromomagnesio)acetylene yield the corresponding ethynylsilacyclanes. Condensation of 1,1-diethynylsilacyclanes or bis(ethynyisilacyclopentyl)ethyne with an equimolar amount of ethylmagnesium bromide and methylbis(trimethylsilylethynyl)fluorosilane gave the corresponding highly unsaturated mono- and binuclear first-generation dendrimers with the cores formed by the silicon atoms incorporated in silacycloalkane fragments. The H-1, C-13, and Si-29 NMR spectra of all the compounds obtained were studied. The key parameters and the chemical graph of the new dendrimers are presented.

  DOI：

  10.1134/s1070363206080172
• 作为产物：
  描述：

  1,5-二溴戊烷 在 四氯化硅 、 magnesium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.5h， 生成 1,1-diethynyl-1-silacyclohexane
  参考文献：
  名称：

  New polyunsaturated organosilicon dendrimers based on 1,1-diethynyl-and 1-vinyl-1-ethynylsilacycloalkanes

  摘要：

  1,1-Dichloro- and 1-vinyl-1-chlorosilacyclanes were prepared by reactions of tetrachlorosilane or vinyltrichlorosilane with magnesium and 1,4-dibromobutane or 1,5-dibromopentane. The reactions of the products obtained with ethynylmagnesium bromide or bis(bromomagnesio)acetylene yield the corresponding ethynylsilacyclanes. Condensation of 1,1-diethynylsilacyclanes or bis(ethynyisilacyclopentyl)ethyne with an equimolar amount of ethylmagnesium bromide and methylbis(trimethylsilylethynyl)fluorosilane gave the corresponding highly unsaturated mono- and binuclear first-generation dendrimers with the cores formed by the silicon atoms incorporated in silacycloalkane fragments. The H-1, C-13, and Si-29 NMR spectra of all the compounds obtained were studied. The key parameters and the chemical graph of the new dendrimers are presented.

  DOI：

  10.1134/s1070363206080172

文献信息

• 4,4-Diorganyl-1,1,3,6-tetrachloro-1,4-tellura(IV)silafulvenes – New class of tellurium–silicon containing heterocycles
  作者：Svetlana V. Amosova、Alexander V. Martynov、Maxim V. Penzik、Natalia A. Makhaeva、Vladimir A. Potapov、Alexander I. Albanov、Larisa V. Zhilitskaya、Mikhail G. Voronkov

  DOI：10.1016/j.jorganchem.2008.05.037

  日期：2008.11

  of the heterocycles have been proved by the multinuclear (1H, 13C, 29Si, 125Te) NMR spectroscopy, 2D NOESY NMR spectroscopy and mass-spectrometry. Z-Isomers are characterized by a long-range spin–spin interaction of protons through five bonds with 5JHH 0.2–0.5 Hz lacking in E-isomers. In the mass spectra the heterocycles manifest themselves as the fragment ions [M−Cl2]+.

  在室温下，TeCl 4与二有机基二乙炔基硅烷RR 1 Si（CCH）2在CHCl 3中的反应导致区域和立体选择性形成一类新的不饱和五元杂环4,4-二有机基-1,1， 3,6-tetrachloro-1,4-tellura（IV）silafulvenes，高产。在硅原子上有二烷基取代基的情况下，反应以100％的立体选择性进行，仅提供E-异构体，而对于环状二乙炔基硅烷，形成的螺杂环具有Z-和E-构型，其中E-异构体占优势。杂环的结构已被多核（1H，13 C，29 Si，125 Te）NMR光谱，2D NOESY NMR光谱和质谱。Z-异构体的特征是质子通过5个键具有5 J HH 0.2-0.5 Hz的E-异构体缺乏长距离自旋自旋相互作用。在质谱图中，杂环表现为碎片离子[M-Cl 2 ] +。
• Unsaturated five-membered selenium–silicon containing heterocycles based on the reactions of selenium di- and tetrahalides with diorganyl diethynyl silanes
  作者：Svetlana V. Amosova、Alexander V. Martynov、Natalia A. Mahaeva、Olga V. Belozerova、Maxim V. Penzik、Alexander I. Albanov、Oleg G. Yarosh、Mikhail G. Voronkov

  DOI：10.1016/j.jorganchem.2006.10.049

  日期：2007.2

  -3-silacyclopentenes-4. The structures of the heterocycles were proved by multinuclear (1H, 13C, 29Si, 77Se) NMR spectroscopy, 2D NOESY NMR spectroscopy and mass-spectrometry. A long-range spin–spin interaction of protons through five bonds lacking in E-isomers was revealed in Z-isomers of fulvene-type heterocycles. In the MS spectra heterocycles of cyclopentene structure were shown to manifest themselves

  室温下，SeBr 2和SeCl 2与二有机基二乙炔基硅烷RR 1 Si（CCH）2在CHCl 3中的反应导致区域和立体选择性形成一类新的不饱和五元杂环4,4- R，R 1 -3,6-二氯（dibromo）-1,4-selenasilafulvenes（Z-异构体为主），制备产率。在相似的条件下，SeBr 4和SeCl 4与二有机基二乙炔基硅烷RR 1 Si（CCH）2的反应继续进行区域选择性反应以提供另一类新的不饱和五元杂环，即2-二氯（二溴）-甲基-2,4-二氯（二溴）-3,3-二有机基-1-硒代-3-硅杂环戊烯-4。通过多核（1 H，13 C，29 Si，77 Se）NMR光谱，2D NOESY NMR光谱和质谱法证明了杂环的结构。在富烯型杂环的Z-异构体中，质子通过E-异构体缺乏的五个键进行了长距离自旋自旋相互作用。在MS光谱中，环戊烯结构的杂环显示为碎片离子[M-HX] +或[MX]
• Heavier Group 14 Congeners of Metalla‐isobenzenes: Access to Metalla‐isosilabenzene and Metalla‐isogermabenzene by <scp>One‐Pot</scp> Reactions
  作者：Jinyu Zhao、Yapeng Cai、Xin Yang、Hong Zhang

  DOI：10.1002/cjoc.202400016

  日期：2024.5.15

  metalla-isogermabenzenes have been successfully synthesized by the formal [5+1]-cycloaddition of diethynylsilane or diethynylgermane with simple metal complexes. This is the first example of a heavier Group 14 metalla-isobenzene isomer bearing a cumulative double bond motif within a metallacycle. These novel complexes were fully characterized by NMR spectroscopy and single-crystal X-ray diffraction

  通过二乙炔基硅烷或二乙炔基锗烷与简单金属配合物的正式[5+1]环加成反应，成功合成了金属异硅苯和金属异锗苯。这是在金属环内带有累积双键基序的较重 14 族金属-异苯异构体的第一个例子。这些新型配合物通过核磁共振波谱和单晶 X 射线衍射分析得到了充分表征。使用密度泛函理论（DFT）计算分析了环状金属-亚乙烯基配合物的稳定性。当带有Si-H键的金属异硅苯用三苯甲基盐作为氢化物清除剂处理时，通过光谱观察到硅阳离子的形成。金属-异硅苯和金属-异锗苯都可以容易地进行迁移插入反应以提供噻咯或锗摩尔。