11,3,5-tris(dimethylsilyl)benzene | 2985-69-5

• 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: 11,3,5-tris(dimethylsilyl)benzene
• 英文别名: 1,3,5-tri(dimethylsilyl)benzene；1,3,5-Tris-dimethylsilyl-benzol；1,3,5-tris(dimethylsilyl)benzene；[3,5-Bis(dimethylsilyl)phenyl]-dimethylsilane
• CAS: 2985-69-5
• 化学式: C₁₂H₂₄Si₃
• 分子量: 252.579
• InChiKey: LHRBHFVFUACXIJ-UHFFFAOYSA-N

物化性质

• 沸点：
  56 °C(Press: 1 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  0.77
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  11,3,5-tris(dimethylsilyl)benzene 在 溴 作用下， 以 四氯化碳 为溶剂， 反应 0.5h， 生成 [3,5-bis[bromo(dimethyl)silyl]phenyl]-bromo-dimethylsilane
  参考文献：
  名称：

  Polycylopentadienyls: Synthesis of arylsilylcyclopentadienyl compounds and their η5-complexes with tungsten

  摘要：

  A general route to arylsilylcyclopentadienyl compounds starting from 1,4-C6H4Br2, 2,6-C5NH3Br2 and 1,3,5-C6H3Br3 is described. The aryl bromides were treated with Mg/ClSiMe2H to give the aryldimethylsilanes 1,4-C6H4(SiMe2H)2, 2,6-C5NH3(SiMe2H)2, and 1,3,5-C6H3(SiMe2H)3 which after reaction with Cl2 or Br2 yielded the aryldimethylsilyl halides 1,4-C6H4(SiMe2Br)2, 2,6-C5NH3 (SiMe2Br)2, 1,3,5-C6H3(SiMe2X)3 (X = Br or Cl) in excellent yields. The halide can be replaced by various cyclopentadienides to give aryldimethylsilylcyclopentadienes of the general type 1,4-C6H4 (SiMe2CP)2 and 1,3,5-C6H3(SiMe2CP)3 (Cp = C5H5 (8,11), C5H3(t-C4H9)2 (9,12), C5HMe4 (10,13)). Compounds C6H5(SiMe2(C5H5)), 1,4-C6H4(SiMe2(C5H5))2 (8) and 1,3,5-C6H3(SiMe2(C5H5))3 (11) were in turn treated with NaH, (MeCN)3W(CO)3, and MeI to give the eta-5-bound complexes C6H5 (SiMe2(C5H4)W(CO)3Me) (14), 1,4-C6H4(SiMe2(C5H4)W(CO)3Me)2 (15), 1,3,5-C6H3(SiMe2(C5H4)-W(CO)3Me)3 (16), which contain up to three half-sandwich units within one molecule.

  DOI：

  10.1016/0022-328x(92)83456-r
• 作为产物：
  描述：

  1,3,5-三溴苯 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 22.0h， 生成 11,3,5-tris(dimethylsilyl)benzene
  参考文献：
  名称：

  [EN] DENTAL COMPOSITIONS CONTAINING CARBOSILANE MONOMERS
  [FR] COMPOSITIONS DENTAIRES CONTENANT DES MONOMERES DE CARBOSILANE

  摘要：

  包含以下结构特征的碳硅烷单体：至少两个Si-芳基键；至少一个（甲基）丙烯酸酯基团；没有Si-O键；最好至少两个硅原子。

  公开号：

  WO2006019801A1

文献信息

• Synthesis of Organosilicon Ligands for Europium (III) and Gadolinium (III) as Potential Imaging Agents
  作者：James I. Bruce、Patrick J. O’Connell、Peter G. Taylor、David P.T. Smith、Roy C. Adkin、Victoria K. Pearson

  DOI：10.3390/molecules25184253

  日期：——

  The relaxivity of MRI contrast agents can be increased by increasing the size of the contrast agent and by increasing concentration of the bound gadolinium. Large multi-site ligands able to coordinate several metal centres show increased relaxivity as a result. In this paper, an “aza-type Michael” reaction is used to prepare cyclen derivatives that can be attached to organosilicon frameworks via hydrosilylation

  MRI 造影剂的弛豫可以通过增加造影剂的尺寸和增加结合钆的浓度来增加。因此，能够协调多个金属中心的大型多位点配体显示出增加的弛豫率。在本文中，“氮杂型迈克尔”反应用于制备可通过氢化硅烷化反应连接到有机硅骨架的环烯衍生物。测试了一系列有机硅骨架，包括倍半硅氧烷笼和二甲基甲硅烷基苯衍生物。具有强吸电子基团的迈克尔供体可用于一步烷基化三个胺中心上的环烯。氢化硅烷化成功地将它们连接到单、二和三二甲基甲硅烷基取代的苯衍生物上。铕和钆配合物的形成和研究使用发光光谱和弛豫。这表明配合物每个镧系元素中心含有两个结合水摩尔，T1弛豫时间测量表明已经实现了弛豫度的增加，特别是对于三取代的支架1,3,5-三（（戊烷-sDO3A）二甲基甲硅烷基）苯- Gd3。这表明弛豫率显着增加（13.1 r1p/mM-1s-1）。
• Unsymmetric main-chain liquid crystal elastomers with tuneable phase behaviour: synthesis and mesomorphism
  作者：Maria Amela-Cortés、Benoît Heinrîch、Bertrand Donnio、Kenneth E. Evans、Chris W. Smith、Duncan W. Bruce

  DOI：10.1039/c0jm03691a

  日期：——

  The synthesis of a new series of polysiloxane-based, main-chain liquid crystal elastomers (MC-LCEs) containing unsymmetric mesogenic units is described. The structure of the mesogenic monomers, spacers and cross-linkers has been varied systematically in order to tune the thermotropic behaviour of the networks. Three unsymmetric mesogens were studied, characterised by having two aromatic rings as the rigid core and two different alkoxy chains. Smectic A or nematic phases were observed, depending on the length of the alkoxy chains. These mesogens were combined with three different spacers, a flexible hexamethyltrisiloxane (S1) and two aromatic bis(dimethylsilyloxy)benzene with the silyl groups disposed para (S2) or meta (S3). To form the MC-LCEs, two cross-linkers were chosen, one flexible 2,4,6,8-tetramethylcyclooctasiloxane (C1) and a rigid, aromatic tris(dimethylsilyl)benzene (C2). The elastomers showed low glass transition temperatures (below 0 °C) and low clearing temperatures (between 30 and 72 °C), as such presenting liquid crystalline properties at room temperature. The transition temperatures could be tuned by a simple choice of the components; for instance, the clearing temperature decreased as aromatic spacers or cross-linkers were introduced. In contrast, the glass transition temperature did not depend on the cross-linker or mesogen used and showed only a small dependence on the structure of the spacer. The phase behaviour of the MC-LCEs was affected greatly by the spacer used and networks containing the trisiloxane spacer systematically exhibited the smectic C phase. The insertion of aromatic spacers favoured the formation of a nematic phase over a smectic phase when the flexible cross-linker, C1, was used. This behaviour was enhanced by the addition of the aromatic cross-linker C3, so that the smectic C phase was suppressed totally and only a nematic phase was observed. The synthesis of the components of MC-LCEs is presented and the structure–thermal properties relationships of the MC-LCEs are discussed.

  描述了一系列含有不对称介晶单元的新型聚硅氧烷基主链液晶弹性体（MC-LCE）的合成。为了调节网络的热致行为，介晶单体、间隔基和交联剂的结构已被系统地改变。研究了三种不对称介晶，其特征是具有两个芳环作为刚性核心和两个不同的烷氧基链。观察到近晶 A 相或向列相，具体取决于烷氧基链的长度。这些介晶与三种不同的间隔基、柔性六甲基三硅氧烷（S1）和两个芳香族双（二甲基硅氧基）苯组合，其中甲硅烷基位于对位（S2）或间位（S3）。为了形成 MC-LCE，选择了两种交联剂，一种是柔性 2,4,6,8-四甲基环八硅氧烷 (C1)，另一种是刚性芳香族三(二甲基甲硅烷基)苯 (C2)。该弹性体表现出低玻璃化转变温度（低于 0 °C）和低澄清温度（30 至 72 °C 之间），因此在室温下呈现液晶特性。转变温度可以通过简单地选择组件来调节；例如，随着芳香族间隔基或交联剂的引入，澄清温度降低。相反，玻璃化转变温度不取决于所使用的交联剂或介晶，并且仅显示出对间隔物的结构的较小依赖性。 MC-LCE 的相行为很大程度上受所用间隔基的影响，并且包含三硅氧烷间隔基的网络系统地表现出近晶 C 相。当使用柔性交联剂 C1 时，芳香族间隔基的插入有利于向列相的形成，而不是近晶相的形成。添加芳香族交联剂 C3 增强了这种行为，从而完全抑制了近晶 C 相，仅观察到向列相。介绍了 MC-LCE 组分的合成，并讨论了 MC-LCE 的结构-热性能关系。
• A sandwich-shaped M₃L₂ zinc(<scp>ii</scp>) complex containing 1,3,5-tris(dimethyl(pyridin-3-yl)silyl)benzene: selective photoluminescence recognition of diiodomethane
  作者：Sangseok Lee、Haeri Lee、Ok-Sang Jung

  DOI：10.1039/c7dt01138e

  日期：——

  The selective small molecular recognition of a discrete sandwich-shaped M₃L₂ zinc(ii) complex showing strong blue photoluminescence has been investigated.

  翻译结果：

  研究了一种选择性小分子识别的离散三明治形状的M₃L₂锌（ii）配合物，该配合物表现出强烈的蓝色光致发光。

• Nanosized starlike molecules. Synthesis and optical properties of tris- and tetrakis[oligo(disilanylenebithienylene)dimethylsilyl]benzene
  作者：Akinobu Naka、Yoshiaki Matsumoto、Tatsuya Itano、Kei Hasegawa、Tomoaki Shimamura、Joji Ohshita、Atsutaka Kunai、Takae Takeuchi、Mitsuo Ishikawa

  DOI：10.1016/j.jorganchem.2008.10.053

  日期：2009.2

  The syntheses of two types of starlike molecules with the arms that extend to three and four directions have been reported. The molecules with the arms consisting of a regular alternating arrangement of a silicon-silicon bond and bithienylene unit that extend to three directions were synthesized by the reactions of 1,3,5-tris(chlorodimethylsilyl) benzene, which was chosen as a core, with the lithio[oligo(disilanylenebithienylene)] derivatives. The starlike molecules with extended arms to four directions were prepared by the reaction of 1,2,4,5-tetrakis(fluorodimethylsilyl) benzene used as a core, with lithio[oligo(disilanylenebithienylene)]s. UV-Vis absorption and fluorescence properties of these starlike molecules have been investigated in a dioxane solution. The present molecules showed absorption maxima in a range of 321-337 nm, and revealed higher fluorescence quantum yields than that of the corresponding linear polymer, poly[(tetraethyldisilanylene) bithiophene]. (C) 2008 Elsevier B.V. All rights reserved.