2,5-dihexyl-4-(triisopropylethynyl)phenylacetylene | 220280-76-2

• 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: 2,5-dihexyl-4-(triisopropylethynyl)phenylacetylene
• 英文别名: 2-(4-Ethynyl-2,5-dihexylphenyl)ethynyl-tri(propan-2-yl)silane
• CAS: 220280-76-2
• 化学式: C₃₁H₅₀Si
• 分子量: 450.823
• InChiKey: YHYVXOPRMFEQJF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.48
• 重原子数：
  32
• 可旋转键数：
  16
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 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：

  2,5-dihexyl-4-(triisopropylethynyl)phenylacetylene 在 bis-triphenylphosphine-palladium(II) chloride 哌啶 、 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 四丁基氟化铵 、 copper(l) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 26.0h， 生成 2-[4-[2-[4-[4-[2,5-Dihexyl-4-[2-[4-(oxan-2-yloxy)phenyl]ethynyl]phenyl]buta-1,3-diynyl]-2,5-dihexylphenyl]ethynyl]phenoxy]oxane
  参考文献：
  名称：

  EPR Probes with Well-Defined, Long Distances between Two or Three Unpaired Electrons

  摘要：

  The synthesis of rod- and star-shaped compounds carrying two or three spin labels as end groups is described. The unpaired electrons are 2.8-5.1 nm apart from each other. The shape-persistent scaffolds were obtained through Pd-Cu-catalyzed alkynyl-aryl coupling and Pd-Cu-catalyzed alkyne dimerization in the presence of oxygen using p-phenyleneethynylene as the basic shape-persistent building block. The spin label 1-oxyl-2,2,5,5-tetramethylpyrroline-3-carboxylic acid (4) was attached through esterification of the terminal phenolic OH groups of the scaffold.

  DOI：

  10.1021/jo005556j
• 作为产物：
  描述：

  1,4-dihexyl-2,5-diiodobenzene 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 哌啶 、 manganese(IV) oxide 、 氢氧化钾 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 2,5-dihexyl-4-(triisopropylethynyl)phenylacetylene
  参考文献：
  名称：

  末端乙炔单元使用不同极性的正交保护基合成单分散低聚（对亚苯基乙炔）

  摘要：

  从 1,4-二己基-2-(3-羟基丙基-1-炔基)-5-[2-(三异丙基甲硅烷基)乙炔基]苯开始，通过发散-收敛合成合成单分散低聚（对亚苯基乙炔基）（oligoPPE）并使用 Pd/Cu 催化的炔-芳基偶联。羟甲基 (HOM) 和三异丙基甲硅烷基 (TIPS) 用作乙炔部分的正交保护基团。极性 HOM 基团对产品的色谱行为有很强的影响，使纯化合物的分离变得非常容易。合成一直进行到九聚体。oligoPPE 被完全表征，包括吸收和发射光谱数据。

  DOI：

  10.1002/(sici)1099-0690(199901)1999:1<277::aid-ejoc277>3.0.co;2-r

文献信息

• Polar tagging in the synthesis of monodisperse oligo(<i>p</i>-phenyleneethynylene)s and an update on the synthesis of oligoPPEs
  作者：Dhananjaya Sahoo、Susanne Thiele、Miriam Schulte、Navid Ramezanian、Adelheid Godt

  DOI：10.3762/bjoc.6.57

  日期：——

  One important access to monodisperse (functionalized) oligoPPEs is based on the orthogonality of the alkyne protecting groups triisopropylsilyl and hydroxymethyl (HOM) and on the polar tagging with the hydroxymethyl moiety for an easy chromatographic separation of the products. This paper provides an update of this synthetic route. For the deprotection of HOM protected alkynes, γ-MnO₂ proved to be better than (highly) activated MnO₂. The use of HOM as an alkyne protecting group is accompanied by carbometalation as a side reaction in the alkynyl–aryl coupling. The extent of carbometalation can be distinctly reduced through substitution of HOM for 1-hydroxyethyl. The strategy of polar tagging is extended by embedding ether linkages within the solubilising side chains. With building blocks such as 1,4-diiodo-2,5-bis(6-methoxyhexyl) less steps are needed to assemble oligoPPEs with functional end groups and the isolation of pure compounds becomes simple. For the preparation of 1,4-dialkyl-2,5-diiodobenzene a better procedure is presented together with the finding that 1,4-dialkyl-2,3-diiodobenzene, a constitutional isomer of 1,4-dialkyl-2,5-diiodobenzene, is one of the byproducts.

  一种重要的单分散（官能化）寡PPEs的获取途径是基于炔基保护基三异丙基硅基和羟甲基（HOM）的正交性，以及使用羟甲基部分标记来实现产物的简便色谱分离。本文提供了这种合成途径的最新更新。对于HOM保护的炔烃的去保护，γ-MnO2被证明比（高度）活化的 更好。使用HOM作为炔基保护基伴随着碳金属化作为炔基-芳基偶联的副反应。通过将HOM替换为1-羟基乙基，可以明显减少碳金属化的程度。极性标记策略通过在溶解侧链中嵌入醚键而得到扩展。使用建筑模块如1,4-二碘-2,5-双(6-甲氧基己基)可减少组装具有官能末端基团的寡PPEs所需的步骤，并使纯化化合物变得简单。对于1,4-二烷基-2,5-二碘苯的制备提出了更好的程序，同时发现1,4-二烷基-2,3-二碘苯，即1,4-二烷基-2,5-二碘苯的构成异构体，是其中的副产物。
• Flexibility of Shape-Persistent Molecular Building Blocks Composed of <i>p-</i>Phenylene and Ethynylene Units
  作者：Gunnar Jeschke、Muhammad Sajid、Miriam Schulte、Navid Ramezanian、Aleksei Volkov、Herbert Zimmermann、Adelheid Godt

  DOI：10.1021/ja102983b

  日期：2010.7.28

  Ethynylene and p-phenylene are frequently employed constitutional units in constructing the backbone of nanoscopic molecules with specific shape and mechanical or electronic function. How well these properties are defined depends on the flexibility of the backbone, which can be characterized via the end-to-end distance distribution. This distribution is accessible by pulse electron paramagnetic resonance (EPR) distance measurements between spin labels that are attached at the backbone. Four sets of oligomer with different sequences of p-phenylene and ethynylene units and different spin labels were prepared using polar tagging as a tool for simple isolation of the targeted compounds. By variation of backbone length, of the sequence of p-phenylene and ethynylene units, and of the spin labels a consistent coarse-grained model for backbone flexibility of oligo(p-phenyleneethynylene)s and oligo(p-phenylenebutadiynylene)s is obtained. The relation of this harmonic segmented chain model to the worm-like chain model for shape-persistent polymers and to atomistic molecular dynamics simulations is discussed. Oligo(p-phenylene butadiynylene)s are found to be more flexible than oligo(p-phenyleneethynylene)s, but only slightly so. The end-to-end distance distribution measured in a glassy state of the solvent at a temperature of 50 K is found to depend on the glass transition temperature of the solvent. In the range between 91 and 373 K this dependence is in quantitative agreement with expectations for flexibility due to harmonic bending. For the persistence lengths at 298 K our data predict values of (13.8 +/- 1.5) nm for poly(p-phenyleneethynylene)s and of (11.8 +/- 1.5) nm for poly(p-phenylenebutadiynylene)s.
• Synthesis of alkynyl(tricarbonyl)rhenium complexes containing a lightly coordinated diamine ligand
  作者：Natalie St. Fleur、J. Craig Hili、Andreas Mayr

  DOI：10.1016/j.ica.2008.07.031

  日期：2009.4

  Several alkynyl(tricarbonyl)diaminerhenium complexes were prepared from corresponding halo complexes and silver acetylides. With the diamine N,N'-dimethylpiperazine the compounds were found to be sufficiently stable to allow synthetic transformations on the acetylide ligand as well as purification by chromatography and subsequent substitution of the diamine ligand by stronger ligands such as phenanthrolines or isocyanides. (C) 2008 Elsevier B.V. All rights reserved.
• Hybrid Composites of Monodisperse π-Conjugated Rodlike Organic Compounds and Semiconductor Quantum Particles
  作者：Volker Hensel、Adelheid Godt、Ronit Popovitz-Biro、Hagai Cohen、Torben R. Jensen、Kristian Kjaer、Isabelle Weissbuch、Efrat Lifshitz、Meir Lahav

  DOI：10.1002/1521-3765(20020315)8:6<1413::aid-chem1413>3.0.co;2-6

  日期：2002.3.15

  Composite materials of quantum particles (Q-particles) arranged in layers within crystalline powders of pi-conjugated, rodlike dicarboxylic acids are reported. The synthesis of the composites, either as three-dimensional crystals or as thin films at the air-water interface, comprises a two-step process: 1) The preparation of the Cd salts 6(Cd), 8(Cd) or Pb salts 6(Pb), 8(Pb) of the oligo(p-phenyteneethynytene)dicarboxylic acids 6(H), 8(H), in which the metal ions are arranged in ribbons and are separated by the long axis of the organic molecules, as demonstrated by X-ray powder diffraction analysis of the solids and grazing incidence X-ray diffraction analysis of the films on water. 2) Topotactic solid/gas reaction of these salts with H2S to convert the metal ions into Q-particles of CdS or PbS embedded in the organic matrix that consists of the acids 6(H) and 8(H). These hybrid materials have been characterized by X-ray photoelectron spectroscopy and transmission electron microscopy.