2-[4-[2-[4-[2-[4-[2-[N,N'-bis[(1R)-1-phenylethyl]carbamimidoyl]-3-[4-(2-trimethylsilylethynyl)phenyl]phenyl]phenyl]ethynyl]phenyl]ethynyl]phenyl]-N,N'-bis[(1R)-1-phenylethyl]-6-[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide | 1034710-58-1

• 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-[4-[2-[4-[2-[4-[2-[N,N'-bis[(1R)-1-phenylethyl]carbamimidoyl]-3-[4-(2-trimethylsilylethynyl)phenyl]phenyl]phenyl]ethynyl]phenyl]ethynyl]phenyl]-N,N'-bis[(1R)-1-phenylethyl]-6-[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide
• CAS: 1034710-58-1
• 化学式: C₉₀H₈₂N₄Si₂
• 分子量: 1275.84
• InChiKey: SEFGXOIMSUEDKJ-PEBOPEEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  21.33
• 重原子数：
  96
• 可旋转键数：
  24
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  48.8
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[4-[2-[4-[2-[4-[2-[N,N'-bis[(1R)-1-phenylethyl]carbamimidoyl]-3-[4-(2-trimethylsilylethynyl)phenyl]phenyl]phenyl]ethynyl]phenyl]ethynyl]phenyl]-N,N'-bis[(1R)-1-phenylethyl]-6-[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide 、 以 氯仿 为溶剂， 生成
  参考文献：
  名称：

  Thermodynamic and Kinetic Stabilities of Complementary Double Helices Utilizing Amidinium–Carboxylate Salt Bridges

  摘要：

  A series of dimer strands consisting of m-terphenyl backbones bearing complementary chiral or achiral amidines and achiral carboxylic acid residues connected by various types of linkers, such as diacetylene, Pt(II)-acetylide, and p-diethynylbenzene linkages, were synthesized by a modular strategy, and their chiroptical properties on the complementary double helix formations were investigated by absorption, circular dichroism (CD), and H-1 NMR spectroscopies. The thermodynamic and kinetic stabilities of the complementary double helices assisted by amidinium-carboxylate salt bridges are highly dependent on their linkages, and the thermodynamic analyses of the dimer duplexes revealed that the association constants increased in the order: Pt(II)-acetylide linker < p-diethynylbenzene linker < diacetylene linker, which is in agreement with the reverse order of their bulkiness. The substituents on the amidine groups were also found to affect the stabilities on the duplexes and the association constants increased in the order: isopropyl < (R)-1-phenylethyl < cyclohexyl. In addition, the introduction of electron-donating and/or electron-withdrawing substituents at the phenyl groups of the p-diethynylbenzene linkers connecting the amidine and carboxylic acid units, respectively, tends to stabilize the complementary double helices, especially in polar solvents, such as DMSO, due to the attractive charge-transfer interactions between the aromatic linkers, although the salt bridge formation is hampered in DMSO. Furthermore, the kinetic analyses of the chain exchange reactions for the duplexes bearing diacetylene and p-diethynylbenzene linkages showed that these were slow processes with negative Delta S-double dagger values, meaning that the chain exchange reactions proceed via direct exchange pathways. In contrast, those for the duplexes bearing Pt(II)-acetylide linkages were fast processes supported by positive Delta S-double dagger values, suggesting that the chain exchange reactions proceed via dissociation-exchange ones. The helix-inversion kinetics investigated for the racernic dimer duplexes composed of achiral amidines based on variable-temperature H-1 NMR measurements indicated that the barriers for the helix-inversion increased in the order: Pt(II)-acetylide linker, p-diethynylbenzene linker < diacetylene linker.

  DOI：

  10.1021/ja303701d
• 作为产物：
  描述：

  、 1,4-二碘苯 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以57%的产率得到2-[4-[2-[4-[2-[4-[2-[N,N'-bis[(1R)-1-phenylethyl]carbamimidoyl]-3-[4-(2-trimethylsilylethynyl)phenyl]phenyl]phenyl]ethynyl]phenyl]ethynyl]phenyl]-N,N'-bis[(1R)-1-phenylethyl]-6-[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide
  参考文献：
  名称：

  Double-Stranded Helical Polymers Consisting of Complementary Homopolymers

  摘要：

  Two complementary homopolymers of chiral amidines and achiral carboxylic acids with m-terphenyl-based backbones were synthesized by the copolymerization of a p-diiodobenzene derivative with the diethynyl monomers bearing a chiral amidine group and a carboxyl group using the Sonogashira reaction, respectively. Upon mixing in THF, the homopolymer strands assembled into a preferred-handed double helix through interstrand amidinium-carboxylate salt bridges, as evidenced by its absorption, circular dichroism, and IR spectra. In contrast, when mixed in less polar solvents, such as chloroform, the complementary strands kinetically formed an interpolymer complex with an imperfect double helical structure containing a randomly hybridized cross-linked structure, probably because of strong salt bridge formations. This primary complex was rearranged into the fully double helical structure by treatment with a strong acid followed by neutralization with an amine. High-resolution atomic force microscopy revealed the double-stranded helical structure and enabled the determination of the helical sense.

  DOI：

  10.1021/ja711447s
• 作为试剂：
  描述：

  2-[4-(2-Anthracen-9-ylethynyl)phenyl]-4-oct-1-ynyl-6-[4-(2-trimethylsilylethynyl)phenyl]benzoic acid 在 2-[4-[2-[4-[2-[4-[2-[N,N'-bis[(1R)-1-phenylethyl]carbamimidoyl]-3-[4-(2-trimethylsilylethynyl)phenyl]phenyl]phenyl]ethynyl]phenyl]ethynyl]phenyl]-N,N'-bis[(1R)-1-phenylethyl]-6-[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide 作用下， 以 氘代氯仿 为溶剂， 反应 0.03h， 以74%的产率得到
  参考文献：
  名称：

  互补盐桥的形成辅助9-苯基乙炔基蒽衍生物的模板定向光二聚化的显着加速†

  摘要：

  在脱气的氯仿和苯中对9-苯基乙炔基蒽的光照射不仅提供了[4 + 2]-抗Diels-Alder加成二聚体，而且还提供了[4 + 4]-抗单晶X射线分析首次发现，β-二聚体是次要产物，而蒽残基在未脱气的稀氯仿中被定量氧化，得到相应的内过氧化物。在存在和不存在互补am二聚体作为模板的情况下，进一步研究了在一端和两端带有9-苯基乙炔基蒽单元的羧酸单体的光化学反应。发现在模板存在下，即使在未脱氯的氯仿中，单体的类似光氧化反应也被显着抑制。此外，在脱气的氯仿中，单-和二-9-苯基乙炔基蒽的结合单体的模板定向光二聚反应显着加速了30倍或61倍，得到了[4 + 2]-抗-和[4 + 4]-抗-二聚体分别作为主要产物和次要产物，而在没有模板的情况下，优先使与二-9-苯基乙炔基蒽结合的单体进行光聚合。

  DOI：

  10.1039/c6ob02087a