cis-(hexaphenyl)(hexahydroxy)cyclohexasiloxane | 154354-98-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cis-(hexaphenyl)(hexahydroxy)cyclohexasiloxane
• 英文别名: Hexahydroxy(hexaphenyl)cyclohexasiloxane；2,4,6,8,10,12-hexahydroxy-2,4,6,8,10,12-hexakis-phenyl-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane
• CAS: 154354-98-0
• 化学式: C₃₆H₃₆O₁₂Si₆
• 分子量: 829.188
• InChiKey: RTXUDZWMVKKNMW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.87
• 重原子数：
  54
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  177
• 氢给体数：
  6
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  cis-(hexaphenyl)(hexahydroxy)cyclohexasiloxane 在 正丁胺 作用下， 以 丙酮 为溶剂， 反应 48.0h， 以18.6%的产率得到氢基-POSS
  参考文献：
  名称：

  硅酸盐/硅醇盐及其水解聚硅醇硅氧烷在多面体低聚倍半硅氧烷 (POSS) 中的合成应用

  摘要：

  Several types of silicate and their hydrolyzed polysilanols were applied to the synthesis of polyhedral oligomeric silsesquioxanes (POSSs). Silicate cubic octasilicate [Si8O20](8-) 5 was silylated with trimethylchlorosilane to yield the incompletely trimethylsilylated cubic octasilicate [Si8O20](SiMe3)(7)H 1b bearing one silanol in addition to the totally trimethylsilylated derivative [Si8O20](SiMe3)(8) 1a. Further silylation of the monosilanol 1b with dimethylchlorosilane and ,-hydridochlorooctamethyltetrasiloxane resulted in the formation of POSSs 1c,d, which have hydrosilyl groups as elongated siloxane side chain. Attempts to generate an amino-substituted POSS via chloromethyldimethylsilylation of silicate 5 followed by reaction with amine as well as lithium amide failed. Amino-substitution was accomplished via the use of amine as a catalyst for the capping reaction of incompletely condensed trisilanol 10b with -aminopropyltrimethoxysilane affording mono amino-functionalized POSSs 2b,c in moderate yields. Another group of silanolates 7-9 was hydrolyzed with AcOH or HCl to give the corresponding cyclic polysilanol siloxanes 11a-c, respectively. Amine-catalyzed condensation of several of these polysilanol siloxanes 11a-c resulted in the formation of POSSs in high yields depending on the structure of substrates.

  DOI：

  10.1002/hc.21373
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 硫化氢 作用下， 以 乙醚 为溶剂， 生成 cis-(hexaphenyl)(hexahydroxy)cyclohexasiloxane
  参考文献：
  名称：

  Zhdanov; Sergienko; Trankina, Doklady Chemistry, 2000, vol. 370, # 1-3, p. 1 - 3

  摘要：

  DOI：

文献信息

• Reaction of the framework 3d-organometallosiloxanes with acetylacetone
  作者：N. V. Sergienko、N. V. Cherkun、V. D. Myakushev、A. A. Korlyukov、B. G. Zavina

  DOI：10.1007/s11172-010-0248-3

  日期：2010.7

  A reaction of acetylacetone with the framework sandwich-type metallosiloxanes (MOS) of general formula [PhSiO2]6M6[PhSiO2]6, where M = Cu, Ni, Mn, was studied by GPC, 1H and 29Si NMR spectroscopy, X-ray diffraction, elemental and functional analysis. The reaction involved replacement of the metal atoms with the hydrogen atoms and is accompanied by the formation of the corresponding chelate complexes M(acac)2. Displacement of the metal from the framework MOS leads to the destruction of molecular skeleton and formation of phenylsiloxanes containing Si-OH groups. The yield and composition of the reaction products considerably depend on the nature of the metal in [PhSiO2]6M6[ThSiO2]6. A selective substitution of the metal leads to the stereoregular hexahydroxyhexaphenylcyclohexasiloxane, [PhSiO(PH)]6, cis-isomer. The structure and composition of the crystalline hexahydroxyhexaphenylcyclohexasiloxane obtained were confirmed by 29Si NMR spectroscopy, X-ray diffraction study, and functional analysis, while its TMS derivative was studied with 1H NMR spectroscopy and GPC. Using a framework manganese phenylsiloxane as an example, a reversible character of the process has been established and an alternative synthesis of this compound from hexahydroxyhexaphenylcyclohexasiloxane and Mn(acac)2 has been accomplished for the first time.

  对通式为[PhSiO2]6M6（其中M = Cu, Ni, Mn）的框架夹心型金属硅氧烷（MOS）与乙酰乙酮的反应进行了研究，使用了GPC、1H和29Si NMR光谱、X射线衍射、元素分析和功能分析。反应过程涉及金属原子被氢原子取代，并伴随形成相应的配位化合物M(acac)2。从框架MOS中取代金属会导致分子骨架的破坏，并形成含有Si-OH基团的苯基硅氧烷。反应产物的产率和组成显著依赖于[PhSiO2]6M6中金属的性质。金属的选择性取代导致了立体规律性的六羟基六苯基环己硅氧烷[PhSiO(PH)]6的顺异构体的形成。所获得的结晶六羟基六苯基环己硅氧烷的结构和组成通过29Si NMR光谱、X射线衍射研究及功能分析得到了确认，而其TMS衍生物则通过1H NMR光谱和GPC进行了研究。以框架锰苯基硅氧烷为例，确立了该过程的可逆特征，并首次完成了从六羟基六苯基环己硅氧烷和Mn(acac)2合成该化合物的替代合成。
• ——
  作者：L. I. Makarova、N. V. Sergienko、E. S. Trankina、A. A. Zhdanov、E. A. Ahmet"eva

  DOI：10.1023/a:1022464802897

  日期：——

  The reactions of [(2-acetoxyetoxy)methyl]dimethylchlorosilane and 1-acetoxy-2-(dimethylchlorosilylmethoxy)benzene with the cage phenylcopper and phenylmanganese siloxanes leads to the cleavage of the M-O-Si bond to give metal chlorides and six-unit cyclosiloxanes with an acetoxy group in the organic substituent at the silicon atom. Methanolysis of these acetoxy derivatives does not affect the ring structure and affords the corresponding polyhydric alcohols.