1,1'-bis(tert-butoxycarbonyl)-4,4'-dibromo-6,6'-di-tert-butyl-2,2'-bibenzimidazole | 1353014-54-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 英文名称: 1,1'-bis(tert-butoxycarbonyl)-4,4'-dibromo-6,6'-di-tert-butyl-2,2'-bibenzimidazole
• CAS: 1353014-54-6
• 化学式: C₃₂H₄₀Br₂N₄O₄
• 分子量: 704.502
• InChiKey: QPJRLTAYVHASAN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.74
• 重原子数：
  42.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  88.24
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  1,1'-bis(tert-butoxycarbonyl)-4,4'-dibromo-6,6'-di-tert-butyl-2,2'-bibenzimidazole 、 9-ethynyltriptycene 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以66%的产率得到1,1,1'-bis(tert-butoxycarbonyl)-4,4'-bis(triptycen-9-ylethynyl)-6,6'-di-tert-butyl-2,2'-bibenzimidazole
  参考文献：
  名称：

  Molecular Spur Gears Comprising Triptycene Rotators and Bibenzimidazole-Based Stators

  摘要：

  Dynamic gearing of molecular spur gears, the most common type of mechanical gear, is elucidated. Molecular design and conformational analysis show that derivatives of 4,4-bis(triptycen-9-ylethynyl)bibenzimidazole represent suitable constructs to investigate gearing behavior of collateral triptycene (Tp) groups. To test this design, DFT calculations (B97-D/Def2-TZVP) were employed and the results suggest that these molecules undergo geared rotation preferentially to gear slippage. Synthesis of derivatives was carried out, providing a series of molecular spur gears, including the first desymmetrized spur gear molecules, which were subsequently subjected to stereochemical analysis.

  DOI：

  10.1021/ja2063346
• 作为产物：
  描述：

  4-叔丁基乙酰苯胺 在 盐酸 、 溴 、 硝酸 、 乙酸酐 、 sodium hydride 、 溶剂黄146 、 tin(ll) chloride 、 potassium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 水 、 mineral oil 为溶剂， 反应 26.0h， 生成 1,1'-bis(tert-butoxycarbonyl)-4,4'-dibromo-6,6'-di-tert-butyl-2,2'-bibenzimidazole
  参考文献：
  名称：

  Molecular Spur Gears Comprising Triptycene Rotators and Bibenzimidazole-Based Stators

  摘要：

  Dynamic gearing of molecular spur gears, the most common type of mechanical gear, is elucidated. Molecular design and conformational analysis show that derivatives of 4,4-bis(triptycen-9-ylethynyl)bibenzimidazole represent suitable constructs to investigate gearing behavior of collateral triptycene (Tp) groups. To test this design, DFT calculations (B97-D/Def2-TZVP) were employed and the results suggest that these molecules undergo geared rotation preferentially to gear slippage. Synthesis of derivatives was carried out, providing a series of molecular spur gears, including the first desymmetrized spur gear molecules, which were subsequently subjected to stereochemical analysis.

  DOI：

  10.1021/ja2063346

文献信息

• Enhanced Gearing Fidelity Achieved Through Macrocyclization of a Solvated Molecular Spur Gear
  作者：Marcus J. Jellen、Ieva Liepuoniute、Mingoo Jin、Christopher G. Jones、Song Yang、Xing Jiang、Hosea M. Nelson、K. N. Houk、Miguel A. Garcia-Garibay

  DOI：10.1021/jacs.1c01885

  日期：2021.5.26

  that favorably position and maintain the two gears in a meshed configuration. Here, we report the synthesis of a new macrocyclic molecular spur gear with a bibenzimidazole stator combined with a second naphthyl bis-gold-phosphine gold complex stator to place two 3-fold symmetric 9,10-diethynyl triptycene cogs at the optimal distance of 8.1 Å for gearing. Micro electron diffraction (μED) analysis confirmed

  具有高齿轮保真度的分子直齿轮动力学可以通过仔细选择构成分子组件来实现，这些组件可以有利地将两个齿轮定位和保持在啮合配置中。在这里，我们报告了一种新的大环分子正齿轮的合成，该齿轮具有联苯并咪唑定子与第二个萘基双-金-膦金复合定子相结合，以将两个 3 倍对称的 9,10-二乙炔基三苯乙烯齿轮放置在 8.1 的最佳距离处Å 用于传动装置。微电子衍射 (μED) 分析证实了大环结构的形成和三苯乙烯齿轮的正确排列。溶液中的传动动力学预计非常快，事实上，速度太快而无法通过使用 CD 2 Cl 的变温1 H NMR观察到2作为溶剂。分子动力学和元动力学模拟的结合预测齿轮传动和滑移的障碍约为。4 kcal mol –1和约。分别为9 kcal mol –1。与非循环模拟相比，该系统的特点是提高了传动装置的保真度。这是通过加固结构实现的，将两个三苯乙烯锁定在优选的传动距离和方向上。