(E)-1,1,6,6-tetrabromo-3,4-bis<(triisopropylsilyl)ethynyl>hexa-1,3,5-triene | 148367-68-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-1,1,6,6-tetrabromo-3,4-bis<(triisopropylsilyl)ethynyl>hexa-1,3,5-triene
• 英文别名: [(3E)-6,6-dibromo-3-(2,2-dibromoethenyl)-4-[2-tri(propan-2-yl)silylethynyl]hexa-3,5-dien-1-ynyl]-tri(propan-2-yl)silane
• CAS: 148367-68-4
• 化学式: C₂₈H₄₄Br₄Si₂
• 分子量: 756.444
• InChiKey: GDCWOTJNFVDCHU-OCEACIFDSA-N

物化性质

• 沸点：
  473.2±45.0 °C(predicted)
• 密度：
  1.341±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.99
• 重原子数：
  34
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  (E)-1,1,6,6-tetrabromo-3,4-bis<(triisopropylsilyl)ethynyl>hexa-1,3,5-triene 在 氯化铵 、 lithium diisopropyl amide 作用下， 生成 硅烷,(3,4-二乙炔基-3-己烯-1,5-二炔-1,6-二基)二[三(1-甲基乙基)-,(E)-
  参考文献：
  名称：

  四乙炔：用于全碳网络和富碳纳米材料的完全交叉共轭的π电子发色团和分子支架

  摘要：

  描述了通过新开发的合成路线制备四乙炔基乙烯（3,4-二乙炔基己基-3-烯-1,5-二炔）1以及多种多样的单，双和三保护的衍生物。这些完全交叉共轭的分子是二维全C网络和具有异常结构和电子特性的新型富含C的纳米结构的通用构建基块和前体，例如具有乙炔基化的膨胀的径向烯，或具有新型聚三乙炔骨架的分子线和聚合物。所有这些路线中的关键一步是Corey-Fuchs醛和酮的二溴代烯烃聚合。甲硅烷基保护的penta-1,4-diyn-3-ones的二溴代烯烃化反应生成相应的二溴代亚甲基衍生物，该衍生物通过两倍的Pd催化的炔烃偶联反应转化为四乙炔基乙烯衍生物。在具有游离顺式或反式-二烯炔基部分的四乙炔的路线中，醛基的二溴代烯烃化反应生成了双晶的二溴代乙烯，在与LDA消除/金属化后，再用H +淬灭或其他亲电子试剂，可以高产率产生游离或取代的乙炔基。四保护基和三保护基四乙炔基是相当稳定的化合物，可以以纯净形式分离

  DOI：

  10.1002/hlca.19950780104
• 作为产物：
  描述：

  triisopropyl((tributylstannyl)ethynyl)silane 在 bis-triphenylphosphine-palladium(II) chloride 、 二异丁基氢化铝 、 三苯基膦 、 pyridinium chlorochromate 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 216.0h， 生成 (E)-1,1,6,6-tetrabromo-3,4-bis<(triisopropylsilyl)ethynyl>hexa-1,3,5-triene
  参考文献：
  名称：

  Anthony, John; Boudon, Corinne; Diederich, Francois, Angewandte Chemie, 1994, vol. 106, # 7, p. 794 - 798

  摘要：

  DOI：

文献信息

• Donor/Acceptor-Substituted Tetraethynylethenes: Systematic Assembly of Molecules for Use as Advanced Materials
  作者：Rik R. Tykwinski、Martin Schreiber、Raquel Pérez Carlón、François Diederich、Volker Gramlich

  DOI：10.1002/hlca.19960790818

  日期：1996.12.11

  such as 11 or 44, in agreement with the presence of highly polarized excited states in these molecules. Correspondingly, fluorescence spectra of TEEs bearing only donor or acceptor substituents showed little solvent dependency. The large majority of the donor/acceptor-substituted TEEs are thermally and environmentally stable molecules. They can be stored for months as solids in the air at room temperature

  制备了带有电子给体（对甲氧基苯基或对氨基苯基）和/或电子接受性（对硝基苯基）基团的一系列全面的四乙炔基（= 3,4-二乙炔基己烯-3-烯-1,5-二炔，TEE）通过[Pd]催化的Sonogashira交叉偶联反应。研究了这些分子的电子和光子特性，并特别强调了由中心TEE核心周围的供体/受体取代程度和模式所引起的影响。该分析表明，分子内供体-受体相互作用（如长波长电荷转移带所证明）在TEE 44和46中显着更有效，反式和顺，线性缀合供体和受体之间的电子通路，比11，与孪位的，交叉共轭的电子通道。UV / VIS光谱揭示的最长波长吸收带（λ的稳定红移最大）作为供体-受体共轭路径的数目在从双-芳基化的变化增加（11，44，和46），以四-芳基化（14 ，31和35）TEE。还发现最长波长吸收的位置强烈依赖于R 2 NC 6 H 4中N-取代基的性质。-捐助团体。电子发射光谱研究表明，供体-受体取
• Molecular Switching: A Fully Reversible, Optically Active Photochemical Switch Based on a Tetraethynylethene‐1,1′‐Binaphthalene Hybrid System
  作者：Luca Gobbi、Paul Seiler、Franc˛ois Diederich、Volker Gramlich

  DOI：10.1002/1522-2675(20000809)83:8<1711::aid-hlca1711>3.0.co;2-#

  日期：2000.8.9

  naphthalene rings of the two 1,1-binaphthalene moieties (Fig. 3). The switching properties were investigated by electronic absorption spectroscopy (Table and Fig. 4): irradiation at λ=398 nm converts trans-isomer (R,R)-1 into cis-isomer (R,R)-2, whereas switching occurs in the opposite direction upon irradiation at λ=323 nm. No thermal interconversion between the two isomers was observed in CH2Cl2 at room

  基于 tetraethynylethene-1,1'-binaphthalene 杂化系统的新型完全可逆光驱动分子开关 (R,R)-1/(R,R)-2 的合成、表征和物理性质被提出。反式构型 (R,R)-1 通过 Stille 交叉偶联在 stannylated tetraethynylethene 3 和 3-iodo-1,1'-binaphthalene 衍生物 (R)-4 之间以 57% 的产率合成（参见方案 2）。顺式异构体 (R,R)-2 通过光异构化由 (R,R)-1 制备。对光开关的顺式和反式都进行了 X 射线晶体结构分析（图 1 和 2）。在结晶状态下，顺式异构体 (R,R)-2 的分子在两个 1,1-联萘部分的萘环之间表现出分子内的边对面 (C−H⋅⋅⋅π) 相互作用（图 2）。 3）。通过电子吸收光谱研究转换特性（表和图 4）：在 λ=398 nm 的照射将反式异构体 (R
• Photoswitchable Tetraethynylethene-Dihydroazulene Chromophores
  作者：Luca Gobbi、Paul Seiler、François Diederich、Volker Gramlich、Corinne Boudon、Jean-Paul Gisselbrecht、Maurice Gross

  DOI：10.1002/1522-2675(20010418)84:4<743::aid-hlca743>3.0.co;2-1

  日期：2001.4.18

  The synthesis. characterization, and photophysical as well as electrochemical properties of the photochromic hybrid systems 11-16 and 18, which contain photoswitchable tetraethynylethene (TEE: 3,4-diethynylhex-3-ene-1,5-diyne) and dihydroazulene (DHA) moieties, are presented. The molecular photoswitches were synthesized by a Sonogashira cross-coupling reaction between an appropriate TEE precursor (6-10 and 17) and an iodinated DHA 1 or its vinylheptafulvene (VHF) isomer (4) (Schemes 5-7). X-Ray crystal structures of five DHA derivatives (1. trans-11a, cis-11a, 12, and 13) are discussed (Figs. 2-5). In all compounds, the cyclohexatriene moiety of the DHA chromophore adopts a clear boat conformation (Table I). presumably due to crystal-packing effects. the arylated TEE moieties in the hybrid systems show substantial distortions from planarity, with the dihedral angles between the plants of the central TEE core and thr adjacent aryl substituents amounting to 43. The switching properties were investigated by electronic absorption spectroscopy. Upon light absorption. DHAs 1. 12-16. and 18 underwent retro-electrocyclization in solution to give the corresponding VHFs( Figs h. II. and 12). The reaction is thermally reversible, with half-lives tau (1,2) between 3.9 and 5.8 h at 2.5 in CH2Cl2 (Figs. 7 and 13 and Table 3). A comparatively slower (E) - (Z) isomerization process about the central C=C bond of the TEE moiety was also observed. The N,N-dimethylanilino-(DMA) substituted TEE-DHA hybrid systems trans-11a and cis-11a did not react to the corresponding VHFs upon irradiation (Scheme 9). Instead. only the reversible (E) - (Z) photoisomerization of the TEE core occurred (Fig. 10 and Table S). This process was further investigated for photofatigue bq electronic-emission spectroscopy (Fig. 17). After protonation of the DMA group, the usual DHA - VHF photoreaction took place. Compound 11 represents a three-way chromophoric molecular switch with three addressable sub-units (TEE core, DHA/VHF moiety, and proton sensitive DMA group) that can undergo individual. reversible switching cycles (Scheme 9). A process modeling the function of an 'AND' logic gate (Fig. 19) and three writc/erase processes could be performed with this system. Cyclic and linear sweep-voltammetry studies in CH2Cl2 (+ Bu4NPF6) revealed the occurrence of characteristic first-reduction steps in the TEE-DHA hybrid systems between - 1.6 and - 1.8 V L'S. Fc/Fc. (ferrocene/ferricinium couple) (Table 5). Oxidations occur at cn. +1.10 V. After photoisomerization to the VHF derivatives. reduction steps at more positive and oxidation steps at mt,re negative potentials H ere recorded. No DHA - VHF isomerization took place upon electrochemical oxidation or reduction (Fig. 20).
• Anthony, John; Knobler, Carolyn B.; Diederich, Francois, Angewandte Chemie, 1993, vol. 105, # 3, p. 437 - 440
  作者：Anthony, John、Knobler, Carolyn B.、Diederich, Francois

  DOI：——

  日期：——
• Anthony John, Boldi Armen M., Rubin Yves, Hobi Markus, Gramlich Volker, K+, Helv. chim. acta, 78 (1995) N 1, S 13-45
  作者：Anthony John, Boldi Armen M., Rubin Yves, Hobi Markus, Gramlich Volker, K+

  DOI：——

  日期：——