1-phenylthio-2,2,3,3,5,5,6,6,7,7,8,8-dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane | 313473-20-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1-phenylthio-2,2,3,3,5,5,6,6,7,7,8,8-dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane
• 英文别名: 2,2,3,3,5,5,6,6,7,7,8,8-Dodecamethyl-1-phenylsulfanyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane
• CAS: 313473-20-0
• 化学式: C₂₀H₄₂SSi₆
• 分子量: 483.132
• InChiKey: NNNXIDJXOZEWBT-UHFFFAOYSA-N

物化性质

• 熔点：
  208-210 °C
• 沸点：
  448.5±45.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-phenylthio-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 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 7.17h， 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-1,4-dicarboxylic acid
  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：

  S-苯基硫代苯基砜 、 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 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以69%的产率得到1-phenylthio-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：

  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

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。