1-adamantylcarbonyloctamethyl-1,4,4-tris-(trimethylsilyl)cyclohexasilane | 1513860-72-4

• 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-adamantylcarbonyloctamethyl-1,4,4-tris-(trimethylsilyl)cyclohexasilane
• 英文别名: 1-Adamantyl-[2,2,3,3,5,5,6,6-octamethyl-1,4,4-tris(trimethylsilyl)hexasilinan-1-yl]methanone；1-adamantyl-[2,2,3,3,5,5,6,6-octamethyl-1,4,4-tris(trimethylsilyl)hexasilinan-1-yl]methanone
• CAS: 1513860-72-4
• 化学式: C₂₈H₆₆OSi₉
• 分子量: 671.601
• InChiKey: YHGPDJZUMVNJQA-UHFFFAOYSA-N

物化性质

• 熔点：
  148-151 °C
• 沸点：
  509.9±33.0 °C(predicted)
• 密度：
  0.92±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.78
• 重原子数：
  38
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-adamantylcarbonyloctamethyl-1,4,4-tris-(trimethylsilyl)cyclohexasilane 以 氘代苯 为溶剂， 反应 4.0h， 生成 [1-Adamantyl-[2,2,3,3,5,5,6,6-octamethyl-4,4-bis(trimethylsilyl)hexasilinan-1-ylidene]methoxy]-trimethylsilane
  参考文献：
  名称：

  Photoinduced Brook-Type Rearrangement of Acylcyclopolysilanes

  摘要：

  Previously unknown 1,1,4-tris(trimethylsilyl)-4-acyldo-decamethylcyclohexasilanes (Me3Si)(2)Si6Me12(Me3Si)COR (16a, R = tert-butyl; 16b, R = 1-adamantyl) have been synthesized by the reaction of the potassium silanides (Me3Si)(2)Si6Me12(Me3Si)K with acid chlorides CICOR, and their photochemical rearrangement reactions have been studied. The molecular structures of 16a,b as determined by single-crystal X-ray diffraction analysis exhibit an unusual twist-boat conformation of the cyclohexasilane ring. When 16a,b were photolyzed with lambda >300 nm radiation, they underwent Brook type 1,3-Si -> 0 migration reactions to generate the cyclohexasilanes 17a,b with exocyclic Si=C bonds along with smaller amounts of the ring-enlarged species 19a,b with endocyclic Si=C double bonds. While 17a,b were stable enough to allow characterization by NMR and UV absorption spectroscopy, the less stable products 19a,b could only be observed in the form of their methanol adducts.

  DOI：

  10.1021/om4009845
• 作为产物：
  描述：

  1,1,4,4-tetrakis(trimethylsilyl)octamethylcyclohexasilane 在 potassium tert-butylate 作用下， 以 乙二醇二甲醚 、 乙醚 为溶剂， 反应 1.5h， 生成 1-adamantylcarbonyloctamethyl-1,4,4-tris-(trimethylsilyl)cyclohexasilane
  参考文献：
  名称：

  Photoinduced Brook-Type Rearrangement of Acylcyclopolysilanes

  摘要：

  Previously unknown 1,1,4-tris(trimethylsilyl)-4-acyldo-decamethylcyclohexasilanes (Me3Si)(2)Si6Me12(Me3Si)COR (16a, R = tert-butyl; 16b, R = 1-adamantyl) have been synthesized by the reaction of the potassium silanides (Me3Si)(2)Si6Me12(Me3Si)K with acid chlorides CICOR, and their photochemical rearrangement reactions have been studied. The molecular structures of 16a,b as determined by single-crystal X-ray diffraction analysis exhibit an unusual twist-boat conformation of the cyclohexasilane ring. When 16a,b were photolyzed with lambda >300 nm radiation, they underwent Brook type 1,3-Si -> 0 migration reactions to generate the cyclohexasilanes 17a,b with exocyclic Si=C bonds along with smaller amounts of the ring-enlarged species 19a,b with endocyclic Si=C double bonds. While 17a,b were stable enough to allow characterization by NMR and UV absorption spectroscopy, the less stable products 19a,b could only be observed in the form of their methanol adducts.

  DOI：

  10.1021/om4009845

文献信息

• Reactivity of Cyclic Silenolates Revisited
  作者：Michael Haas、Mario Leypold、Lukas Schuh、Roland Fischer、Ana Torvisco、Harald Stueger

  DOI：10.1021/acs.organomet.7b00540

  日期：2017.10.9

  behavior is also reflected by the reaction of 2a,c with MeI. Both alkylation reactions take place at the corresponding silicon atom and lead to the formation of the methylated structures 4a,b in nearly quantitative yields. Furthermore, the thermal stability of exocyclic silenolates 2a,c was investigated. In the case of 2a, a thermally induced intramolecular sila-Peterson alkenation was observed at 60 °C

  稳定的环外硅酸盐2a – c（2a，R = Mes; 2b，R = o- Tol; 2c，R = 1-Ad）已通过NMR和UV-vis光谱进行了全面表征。根据光谱和结构特征，2a - c最好描述为溶液中的酰基甲硅烷基阴离子（互变异构结构I）。2a，c与MeI的反应也反映了这种行为。两种烷基化反应均发生在相应的硅原子处，并导致形成甲基化结构4a，b以几乎定量的产量。此外，研究了环外硅酸盐2a，c的热稳定性。在2a的情况下，在60°C时观察到热诱导的分子内sila-Peterson烯化。这种转变允许直接进入2-氧杂六硅双环[3.2.1] octan-8-ide 5，作为结构复杂的双环硅骨架。与此相反，加热2c（作为烷基取代的硅烷基化物的一个例子）导致意外降解为未表征的聚合物。但是，我们能够分离出1-金刚烷基取代的双环化合物8，该化合物在结构上与5密切相关通过用1当量的1-金刚烷酰氯处理1,4-二钾-1
• Synthesis and characterization of cyclic acylsilanes
  作者：Michael Haas、Lukas Schuh、Ana Torvisco、Harald Stueger、Christa Grogger

  DOI：10.1080/10426507.2015.1128924

  日期：2016.4.2

  GRAPHICAL ABSTRACT ABSTRACT Acylcyclohexasilanes are interesting starting materials for the formation of cyclic silenes. Employing standard cyclopolysilane synthetic procedures, nine previously unknown acylcyclohexasilanes were synthesized and characterized by NMR, and UV-Vis spectroscopy and X-ray crystallography to elucidate substituent influences of the R-group attached to the carbonyl C-atom.

  图形摘要 摘要 酰基环己硅烷是形成环状硅烯的重要原料。采用标准的环聚硅烷合成程序，合成了九种以前未知的酰基环己硅烷，并通过 NMR、UV-Vis 光谱和 X 射线晶体学进行表征，以阐明连接到羰基 C 原子上的 R 基团的取代基影响。
• Synthesis of Stable Dianionic Cyclic Silenolates and Germenolates
  作者：Tanja Wiesner、Mario Leypold、Anja Steinmaurer、Dominik Schnalzer、Roland C. Fischer、Ana Torvisco、Michael Haas

  DOI：10.1021/acs.organomet.0c00385

  日期：2020.8.10

  The reaction of 2b with ClSiMe2SiMe2Cl led to the formation of the acyl bicyclo[2.2.2]octasilane 6. Moreover, the reaction of 2a,b and 4a,b with MeI, as an example of a carbon-centered electrophile, led to selective alkylation reactions at the negatively charged silicon and germanium atoms. The corresponding methylated structures 9a,b and 10a,b were formed in nearly quantitative yields. The competitive

  在这一贡献中，描述了一种便利的合成方法，以获得先前未知的双阴离子环状硅烯酸酯和种烯酸酯。这些二价阴离子2a，b和4a，b可容易地通过一锅法合成方案以高产率获得。通过NMR，单晶X射线晶体学和DFT量子力学计算的组合分析了它们的结构特性。此外，研究了2a，b和4a，b与亲电试剂的选定实例的反应性。2a和4a与ClSi i Pr反应图3给出具有环外双键的聚硅烷和聚锗烷的新实例。2b与ClSiMe 2 SiMe 2 Cl的反应导致形成酰基双环[2.2.2]八硅烷6。此外，作为碳中心亲电体的一个例子，2a，b和4a，b与MeI的反应导致带负电的硅和锗原子发生选择性烷基化反应。相应的甲基化结构9a，b和10a，b以几乎定量的产量形成。甲硅烷基和甲硅烷基阴离子对1当量的ClSiMe 3的竞争反应性表明，反应的结果受到羰基部分取代基的强烈影响。图2a与1个当量的ClSiMe反应3，得到相应的环状silenolate
• Stable Silenolates and Brook-Type Silenes with Exocyclic Structures
  作者：Michael Haas、Roland Fischer、Michaela Flock、Stefan Mueller、Martin Rausch、Robert Saf、Ana Torvisco、Harald Stueger

  DOI：10.1021/om500935r

  日期：2014.11.10

  The first silenolates with exocyclic structures [(Me₃Si)₂Si(Si₂Me₄)₂SiC(R)O]^-K⁺ (2a: R = 1-adamantyl; 2b: mesityl; 2c: o-tolyl) were synthesized by the reaction of the corresponding acylcyclohexasilanes 1a-c with KOtBu. NMR spectroscopy and single-crystal X-ray diffraction analysis suggest that the aryl-substituted silenolates 2b,c exhibit increased character of functionalized silenes as compared to the alkyl-substituted derivative 2a due to the different coordination of the K⁺ counterion to the SiC(R)O moiety. 2b,c, thus, reacted with ClSiiPr₃ to give the exocyclic silenes (Me₃Si)₂Si(Si₂Me₄)₂Si=C(OSiiPr₃)R (3b: R = Mes; 3c: o-Tol), while 2a afforded the Si-silylated acylcyclohexasilane 1d. The thermally remarkably stable compound 3b, which is the first isolated silene with the sp² silicon atom incorporated into a cyclopolysilane framework, could be fully characterized structurally and spectroscopically.