2,2,3,3,5,5,6,6,7,7,8,8-dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane | 218932-30-0

• 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: 2,2,3,3,5,5,6,6,7,7,8,8-dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane
• CAS: 218932-30-0
• 化学式: C₁₄H₃₈Si₆
• 分子量: 374.969
• InChiKey: KVMUSHZLHRUINX-UHFFFAOYSA-N

物化性质

• 沸点：
  333.8±42.0 °C(Predicted)
• 密度：
  0.85±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  3.0
• 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：

  2,2,3,3,5,5,6,6,7,7,8,8-dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane 在 正丁基锂 、 偶氮二甲酸二异丙酯 、 potassium tert-butylate 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 生成 (E)-pent-2-enyl 2,2,3,3,5,5,6,6,7,7,8,8-dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane-1-carboxylate
  参考文献：
  名称：

  2,3,5,6,7,8-Hexasilabicyclo[2.2.2]octane-1-carboxylic acids and esters: preparation and structure

  摘要：

  Polysilacage acid HC(SiMe2SiMe2)(3)CCO2H was prepared quantitatively by deprotonation of HC(SiMe2SiMe2)(3)CH by a superbase in excess followed by trapping with CO2. The acid allowed to disclose X-ray analysis of hydrogen-bonded dimers that preferred pairs of the same enantiomeric isomers. Cage diacid HO2CC(SiMe2SiMe2)(3)CCO2H also was prepared. Esterification of the acids was found to proceed in good yields via the Mitsunobu conditions using diisopropyl azodicarboxylate. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(03)00161-x
• 作为产物：
  描述：

  Bis(phenylsulfanyl)methyl-[bis(phenylsulfanyl)methyl-dimethylsilyl]-dimethylsilane 在 LiDBB 作用下， 以 四氢呋喃 为溶剂， 生成 2,2,3,3,5,5,6,6,7,7,8,8-dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane
  参考文献：
  名称：

  新型笼式聚碳硅烷。十二甲基-2,3,5,6,7,8-六硅杂双环[2.2.2]辛烷及其衍生物的制备与表征

  摘要：

  合成了2,2,3,3,5,5,6,6,7,7,8,8-十二甲基-2,3,5,6,7,8-六硅杂双环[2.2.2]辛烷(1)首次通过三个步骤以 56% 的总产率通过三个二氯二甲基乙硅烷分子的三个二氯二甲基乙硅烷分子从双（苯硫基）甲烷衍生的两个三阴离子分子中进行三重甲硅烷基化。X 射线分析表明 1 的分子结构与理想的双环 [2.2.2] 辛烷骨架略有扭曲。描述了 1 的衍生化和这些化合物的紫外光谱。

  DOI：

  10.1246/cl.1998.1145

文献信息

• Preparation and Structure of Alkenyl- and Alkynyl-Substituted Polysilamod­ules HC(SiMe₂SiMe₂)₃CR
  作者：Masaki Shimizu、Hirofumi Mizukoshi、Tamejiro Hiyama

  DOI：10.1055/s-2004-822394

  日期：——

  Facile methods for the introduction of alkenyl and alkynyl groups at the bridgehead position of polysilamodule HC(SiMe2SiMe2)3CH are established. Deprotonation of the module with BuLi/t-BuOK in THF at -40 °C followed by alkylation with bromoacetaldehyde diethyl acetal gives the corresponding acetal, which was hydrolyzed with zinc chloride, yielding a formylmethyl-substituted cage compound. Treatment of the aldehyde with triflic anhydride in the presence of 2,6-di-t-butyl-3-methylpyridine produced the corresponding enol triflate consisting of a 4:1 mixture of E and Z isomers. Palladium-catalyzed cross-coupling of the triflate with organometallic reagents afforded alkenyl group-substituted cage molecules in good yields. Meanwhile, lithiation of phenylthio-substituted cage derivative with lithium 4,4′-di-tert-butylbiphenylide in THF followed by transmetalation with copper iodide and subsequent coupling with iodoalkynes allowed us to prepare alkynyl-substituted polysilacage compounds. The structures were determined by X-ray diffraction of single crystals.

  建立了在多硅模块 HC(SiMe2SiMe2)3CH 的桥头位置引入烯基和炔基的简便方法。首先在 -40 °C 下用 BuLi/t-BuOK 在 THF 中去质子化该模块，然后用溴乙醛二乙基缩醛进行烷基化，得到相应的缩醛，随后用氯化锌水解，得到一种甲酰基甲基取代的笼状化合物。将该醛与三氟化酸酐在 2,6-二-叔丁基-3-甲基吡啶的存在下反应，生成相应的烯醇三氟甲基酯，包含 4:1 的 E 和 Z 异构体混合物。经过钯催化的三氟甲基酯与有机金属试剂的交叉耦合反应，获得了烯基取代的笼状分子，产率良好。同时，使用锂 4,4'-二叔丁基联苯负离子在 THF 中对苯硫取代的笼衍生物进行锂化，随后与碘化铜进行转金属化，再与碘炔进行耦合，成功制备了炔基取代的多硅笼化合物。通过单晶 X 射线衍射确定了这些结构。
• Selenium‐Substituted Phosphaalk­enes Obtained through 1,2‐Elimination of Chlorosilanes from Selenen­ylchlorophosphines
  作者：Takahiro Sasamori、José Manuel Villalba Franco、Jing‐Dong Guo、Koh Sugamata、Shigeru Nagase、Rainer Streubel、Norihiro Tokitoh

  DOI：10.1002/ejic.201500989

  日期：2016.2

  bearing a silylalkyl group, were synthesized. Subsequent treatment with Lewis acids such as AlCl3 afforded the corresponding phosphaalkenes. A reaction mechanism that proceeds through an intramolecular 1,2-elimination of chlorosilane was proposed.

  合成了带有甲硅烷基烷基的稳定硒基氯膦。随后用路易斯酸如 AlCl3 处理得到相应的磷烯烃。提出了通过氯硅烷的分子内 1,2-消除进行的反应机制。
• 1-Alkyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octanes: Unconventional Class of Mesomorphic Columnar Compounds
  作者：Masaki Shimizu、Masanori Nata、Kenji Mochida、Tamejiro Hiyama、Seiji Ujiie、Masafumi Yoshio、Takashi Kato

  DOI：10.1002/anie.200604170

  日期：2007.4.20
• Novel Cage Polycarbosilanes. Preparation and Characterization of Dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane and Its Derivatives
  作者：Masaki Shimizu、Naoko Inamasu、Yasushi Nishihara、Tamejiro Hiyama

  DOI：10.1246/cl.1998.1145

  日期：1998.11

  8-Dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane (1) was synthesized for the first time via three steps in 56% overall yield through triple silylation with three dichlorodimethyldisilane molecules of two trianionic molecules derived from bis(phenylthio)methane. The molecular structure of 1 was shown to be slightly distorted from an ideal bicyclo[2.2.2]octane skeleton by X-ray analysis. The derivatization

  合成了2,2,3,3,5,5,6,6,7,7,8,8-十二甲基-2,3,5,6,7,8-六硅杂双环[2.2.2]辛烷(1)首次通过三个步骤以 56% 的总产率通过三个二氯二甲基乙硅烷分子的三个二氯二甲基乙硅烷分子从双（苯硫基）甲烷衍生的两个三阴离子分子中进行三重甲硅烷基化。X 射线分析表明 1 的分子结构与理想的双环 [2.2.2] 辛烷骨架略有扭曲。描述了 1 的衍生化和这些化合物的紫外光谱。
• 2,3,5,6,7,8-Hexasilabicyclo[2.2.2]octane-1-carboxylic acids and esters: preparation and structure
  作者：Masaki Shimizu、Susumu Sugimoto、Hirofumi Mizukoshi、Tamejiro Hiyama

  DOI：10.1016/s0022-328x(03)00161-x

  日期：2003.11

  Polysilacage acid HC(SiMe2SiMe2)(3)CCO2H was prepared quantitatively by deprotonation of HC(SiMe2SiMe2)(3)CH by a superbase in excess followed by trapping with CO2. The acid allowed to disclose X-ray analysis of hydrogen-bonded dimers that preferred pairs of the same enantiomeric isomers. Cage diacid HO2CC(SiMe2SiMe2)(3)CCO2H also was prepared. Esterification of the acids was found to proceed in good yields via the Mitsunobu conditions using diisopropyl azodicarboxylate. (C) 2003 Elsevier Science B.V. All rights reserved.