6-(3,5-di(tert-butyl)phenyl)-4-(3,5-di(tert-butyl)phenylethynyl)-1-trimethylsilyl-3-trimethylsilylethynylhex-3-ene-1,5-diyne | 159461-30-0

• 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: 6-(3,5-di(tert-butyl)phenyl)-4-(3,5-di(tert-butyl)phenylethynyl)-1-trimethylsilyl-3-trimethylsilylethynylhex-3-ene-1,5-diyne
• 英文别名: 1-[3,5-Di(tert-butyl)phenyl]-3-{[3,5-di(tert-butyl)phenyl]ethynyl}-4-[(trimethylsilyl)ethynyl]-6-(trimethylsilyl)hex-3-ene-1,5-diyne；[6-(3,5-ditert-butylphenyl)-4-[2-(3,5-ditert-butylphenyl)ethynyl]-3-(2-trimethylsilylethynyl)hex-3-en-1,5-diynyl]-trimethylsilane
• CAS: 159461-30-0
• 化学式: C₄₄H₆₀Si₂
• 分子量: 645.131
• InChiKey: BWQRVXKODFKANY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.34
• 重原子数：
  46.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  6-(3,5-di(tert-butyl)phenyl)-4-(3,5-di(tert-butyl)phenylethynyl)-1-trimethylsilyl-3-trimethylsilylethynylhex-3-ene-1,5-diyne 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 水 、 三乙胺 为溶剂， 反应 50.0h， 生成 1-[3,5-di(tert-butyl)phenyl]-3-[2-[3,5-di(tert-butyl)phenyl]ethynyl]-4-[2-(2-thienyl)ethynyl]-6-(2-thienyl)hex-3-ene-1,5-diyne
  参考文献：
  名称：

  Donor-Acceptor-Functionalized Tetraethynylethenes with Nitrothienyl Substituents: Structure-Property Relationships

  摘要：

  Tetraethynylethenes (TEEs) functionalized with donor (4-(dimethylamino)phenyl) and acceptor (5-nitro-2-thienyl) groups were prepared by Pd-0-catalyzed Sonogashira cross-coupling reactions (Schemes 1-6). The physical properties of these novel chromophores were examined and compared with those of analogous systems containing 4-nitrophenyl instead of 5-nitro-2-thienyl acceptor groups. X-Ray crystal-structure analyses showed the pi-conjugated frameworks of 2, 11, and 13, including the TEE core and all aryl moieties, to be nearly perfectly planar (Figs. 1, 3, and 4). Ln contrast, one 4-(dimethylamino)phenyl group in 10 is rotated almost 90 degrees out of the molecular plane, presumably due to crystal-packing effects (Fig. 2). The analysis of bond lengths and bond angles revealed little, if any, evidence of intramolecular ground-state donor-acceptor interactions. The electrochemical behavior of nitrothienyl-substituted TEEs is similar to that of the corresponding nitrophenyl-functionalized derivatives (Table 3). The nitrothienyl groups were reduced at -1.23 V (vs. the ferrocene/ferricinium couple, Fc/Fc(+)), regardless of the degree or pattern of other substitutions. For nonsymmetrical TEE 13, the reduction of the nitrothienyl group at - 1.23 V is followed by a reduction of the nitrophenyl group at - 1.40 V, a potential typical for the reduction of other nitrophenyl-substituted TEEs, such as 17-20. UV/VIS Spectroscopy showed a consistently lower-energy absorption cutoff for nitrothienyl derivatives compared with the analogous nitrophenyl-substituted TEEs that confirms a lowering of the HOMO-LUMO gap as a result of nitrothiophene substitution (Figs. 5 and 6). A comparison of the tetrakis-arylated TEEs 11, 13, and 20 clearly showed a steady bathochromic shift of the longest-wavelength absorption maximum and the end-absorption upon sequential replacement of nitrophenyl by nitrothienyl groups. Quantum-chemical computations were performed to explain a number of complex features of the electronic absorption spectra. All empirical features of relevance in the experimental UV/VIS spectra for 2, 5, 6, and 17-19 were correctly reproduced by computation (Tables 4 and 5). The combination of theory and experiment was found to be very useful to explain the particular acceptor properties of the 5-nitro-2-thienyl group.

  DOI：

  10.1002/1522-2675(20000705)83:7<1484::aid-hlca1484>3.0.co;2-1
• 作为产物：
  描述：

  1,3-di-tert-butyl-5-ethynylbenzene 、 3-(dibromomethylidene)-1,5-bis(trimethylsilyl)penta-1,4-diyne 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 正丁胺 作用下， 以 苯 为溶剂， 反应 48.0h， 以33%的产率得到6-(3,5-di(tert-butyl)phenyl)-4-(3,5-di(tert-butyl)phenylethynyl)-1-trimethylsilyl-3-trimethylsilylethynylhex-3-ene-1,5-diyne
  参考文献：
  名称：

  Faust, Ruediger; Diederich, Francois; Gramlich, Volker, Chemistry - A European Journal, 1995, vol. 1, # 2, p. 111 - 117

  摘要：

  DOI：

文献信息

• Highly Functionalized Dimeric Tetraethynylethenes and Expanded Radialenes: Strong Evidence for Macrocyclic Cross-Conjugation
  作者：Mogens Brøndsted Nielsen、Martin Schreiber、Yong Gu Baek、Paul Seiler、Steve Lecomte、Corinne Boudon、Rik R. Tykwinski、Jean-Paul Gisselbrecht、Volker Gramlich、Philip J. Skinner、Christian Bosshard、Peter Günter、Maurice Gross、François Diederich

  DOI：10.1002/1521-3765(20010803)7:15<3263::aid-chem3263>3.0.co;2-3

  日期：2001.8.3

  A selection of dimeric tetra-ethynylethenes (TEEs) and perethynylated expanded radialenes, containing different donor/acceptor substitution patterns, have been prepared and fully characterized. The first X-ray crystal structure of an expanded [6]radialene, with twelve peripheral 3,5-di(tert-butyl)phenyl substituents, is presented. This macrocycle, the all-carbon core of which is isomeric with fullerene C-60, adopts a non-planar, "chair-like" conformation. Also a TEE dimer, carrying NN-dimethylaniline donor substituents, has been subjected to an X-ray crystallo graphic analysis. The electronic properties were studied by UV/Vis spectroscopy and electrochemistry, providing fundamental insight into mechanisms of pi -electron delocalization in the acyclic and macrocyclic chromophores. Donor or donor-acceptor-substituted dimeric TEE derivatives show very strong absorptions extending over the entire UV/Vis region; their longest wavelength absorption bands have high charge-transfer character. Macrocyclic cross-conjugation in the expanded radialenes becomes increasingly efficient with increasing donor-acceptor polarization. A dual, strongly solvent-polarity-dependent fluorescence was observed for a tetrakis(NN-dimethylaniline)-substituted dimeric TEE; this interesting emission behavior is explained by the twisted intramolecular charge-transfer (TICT) state model. Donor-substituted expanded radialenes display huge resonance-enhanced third-order nonlinear optical coefficients.