1-Chlor-3,5,7-trimethyl-1,3,5,7-tetrasila-adamantan | 30038-39-2

• 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-Chlor-3,5,7-trimethyl-1,3,5,7-tetrasila-adamantan
• 英文别名: 1-Chloro-3,5,7-trimethyl-1,3,5,7-tetrasilatricyclo[3.3.1.13,7]decane
• CAS: 30038-39-2
• 化学式: C₉H₂₁ClSi₄
• 分子量: 277.061
• InChiKey: WDBGOCLDHLINCH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 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-Chlor-3,5,7-trimethyl-1,3,5,7-tetrasila-adamantan 在 溴 、 苄基三甲基氢氧化铵 、 二异丁基氢化铝 、 环己基铵氟化物 作用下， 以 四氯化碳 、 乙醚 、 氯仿 为溶剂， 生成 1-fluoro-3,5,7-trimethyl-1,3,5,7-tetrasila-adamantane
  参考文献：
  名称：

  Reactivity studies of bridgehead organosilicon compounds with nucleophilic reagents

  摘要：

  DOI：

  10.1021/ja00804a026
• 作为产物：
  描述：

  1,3,5,7-tetramethyl-1,3,5,7-tetrasilaadamantane 在 aluminum tri-bromide 、 一氯化碘 作用下， 以 四氯化碳 为溶剂， 反应 48.0h， 以73%的产率得到1-Chlor-3,5,7-trimethyl-1,3,5,7-tetrasila-adamantan
  参考文献：
  名称：

  1-Triflato-3,5,7-trimethyl-1,3,5,7-tetrasilaadamantane and 1,3-bis-triflato-5,7-dimethyl-1,3,5,7-tetrasilaadamantane; synthesis, complexation study and X-ray structure of 1-hydroxy-3,5,7-trimethyl-1,3,5,7-tetrasilaadamantane

  摘要：

  The symmetrical 1,3,5,7-tetramethyl-1,3,5,7-tetrasilaadamantane (1) reacts with 1.5 molar equivalents of ICl-AgOTf at room temperature to furnish the hitherto unknown 1-triflato-3,5,7-trimethyl-1,3,5,7-tetrasilaadamantane (9) chemoselectively, in near quantitative yields. The treatment of 9 with 2 mol equivalents of ICl-AgOTf affords the bis-triflate 10 in high yields. Control experiments showed that reaction of 1 with ICl (1 mol equivalents) -CCl4 is sluggish, giving 18% conversion to 1-chloro-3,5,7-trimethyl-1,3,5,7-tetrasilaadamantane (2) after 23 h at room temperature. Addition of AlBr3 catalyzes the process, allowing 73%, conversion after 21 h at room temperature. The ICI-AgOTf reagent eliminates the need to prepare and isolate 2 as an intermediate for the synthesis of 9. In silicon NMR spectra, the Si-29 Si-OTf resonance of 10 is slightly upfield compared with that of 9. Treatment of 9 with a saturated solution of B(C6F5)(3) in CH2Cl2 at room temperature shows only minor deshielding at silicon as determined by Si-29-NMR spectroscopy. Attempts to generate donor-acceptor complexes by treatment of 9 with AI(OTf)(3)-CD3CN and with liquid BCl3 gave no notable changes in the Si-OTf NMR chemical shift. In attempts to grow crystals from 9 and 10, white crystals suitable for X-ray analysis were obtained from a sample of 9, the molecular structure of which was shown to be 1-hydroxy-3,5,7-trimethyl-1,3,5,7-tetra-silaadamantane (11), generated by hydrolysis of the Si-OTf bond. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)01642-x

文献信息

• Synthesis and Structure of the First Bridgehead Silylium Ion
  作者：Rudolf J. Wehmschulte、Kenneth K. Laali、Gabriela L. Borosky、Douglas R. Powell

  DOI：10.1021/om5003792

  日期：2014.5.12

  We report the first successful synthesis of the long-sought arene-solvated bridgehead silylium ion [Si4Me3(CH2)6][CHB11Cl11] by hydride abstraction from the tetrasilaadamantyl derivative HSi4Me3(CH2)6 with the trityl salt [Ph3C][CHB11Cl11] in toluene, benzene, or bromobenzene solution. The silylium···arene complex was characterized by X-ray diffraction analysis and by NMR spectroscopy and was studied

  我们报道了通过从四硅烷基金刚烷基衍生物HSi 4 Me 3（CH 2）6提取氢化物首次成功合成了长寻求的芳烃溶剂化桥头硅烷基离子[Si 4 Me 3（CH 2）6 ] [CHB 11 Cl 11 ]。三苯甲基盐[Ph 3 C] [CHB 11 Cl 11]溶于甲苯，苯或溴苯溶液中。通过X射线衍射分析和NMR光谱对硅烷基芳烃配合物进行表征，并进行了计算研究。NMR研究表明，甲硅烷基物质在BrPh / MePh混合溶剂中经历了动态的溶剂化物交换。
• Corborundanes. II. Derivative chemistry of a very reluctantly reactive bridgehead silicon center
  作者：C. L. Frye、J. M. Klosowski

  DOI：10.1021/ja00775a072

  日期：1972.10