8,8,14,14-Tetramethyl-1-borahexacyclo[11.7.1.13,19.02,7.09,21.015,20]docosa-2,4,6,9(21),10,12,15,17,19-nonaene | 1362852-14-9

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 8,8,14,14-Tetramethyl-1-borahexacyclo[11.7.1.13,19.02,7.09,21.015,20]docosa-2,4,6,9(21),10,12,15,17,19-nonaene
• 英文别名: 8,8,14,14-tetramethyl-1-borahexacyclo[11.7.1.13,19.02,7.09,21.015,20]docosa-2,4,6,9(21),10,12,15,17,19-nonaene
• CAS: 1362852-14-9
• 化学式: C₂₅H₂₃B
• 分子量: 334.269
• InChiKey: QXWFGSLOBVNTJS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.39
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.28
• 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：

  8,8,14,14-Tetramethyl-1-borahexacyclo[11.7.1.13,19.02,7.09,21.015,20]docosa-2,4,6,9(21),10,12,15,17,19-nonaene 在 chromium(VI) oxide 、 四氯化钛 、 溶剂黄146 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 13.5h， 生成 8,8,14,14,22,22-Hexamethyl-1-borahexacyclo[11.7.1.13,19.02,7.09,21.015,20]docosa-2,4,6,9(21),10,12,15,17,19-nonaene
  参考文献：
  名称：

  JP5959171

  摘要：

  公开号：
• 作为产物：
  描述：

  9-[2,6-di(propen-2-yl)phenyl]-9,10-dihydro-9-boraanthracene 在 Sc(OTf)3 作用下， 以 1,2-二氯乙烷 为溶剂， 以68%的产率得到8,8,14,14-Tetramethyl-1-borahexacyclo[11.7.1.13,19.02,7.09,21.015,20]docosa-2,4,6,9(21),10,12,15,17,19-nonaene
  参考文献：
  名称：

  Planarized Triarylboranes: Stabilization by Structural Constraint and Their Plane-to-Bowl Conversion

  摘要：

  Triphenylborane and 9,10-diphenyl-9,10-dihydro-9,10-diboraanthracene, constrained to a planar arrangement with methylene tethers, were synthesized by intramolecular multi-fold Friedel-Crafts cyclization. These compounds were stable toward air, water, and amines, despite the absence of steric protection in the vertical direction with respect to the B atoms, and showed characteristic structural, electronic, and photophysical properties. In addition, upon treatment with a fluoride ion, these compounds underwent a plane-to-bowl conversion in a controlled manner.

  DOI：

  10.1021/ja211944q

文献信息

• Boracyclophanes: Modulation of the σ/π Character in Boron-Benzene Interactions
  作者：Tomokatsu Kushida、Shigehiro Yamaguchi

  DOI：10.1002/anie.201303830

  日期：2013.7.29

  Character sketch: Boracyclophanes, in which the benzene ring coordinates to the boron atom, were synthesized. X‐ray crystallographic analysis and theoretical calculations revealed the intrinsic character of the boron–benzene interaction. Its σ/π character can be modulated by changing the electron‐donating character of the benzene ring.

  人物素描：合成了苯环环，其中苯环与硼原子配位。X射线晶体学分析和理论计算揭示了硼与苯相互作用的内在特征。可以通过改变苯环的供电子特性来调节其σ/π特性。
• Constraint-induced structural deformation of planarized triphenylboranes in the excited state
  作者：Tomokatsu Kushida、Cristopher Camacho、Ayumi Shuto、Stephan Irle、Masayasu Muramatsu、Tetsuro Katayama、Syoji Ito、Yutaka Nagasawa、Hiroshi Miyasaka、Eri Sakuda、Noboru Kitamura、Zhiguo Zhou、Atsushi Wakamiya、Shigehiro Yamaguchi

  DOI：10.1039/c3sc52751d

  日期：——

  Triphenylboranes planarized with three methylene bridges exhibited dual fluorescence bands around 340 and 400 nm despite their structural constraint. To elucidate the origin, their excited state dynamics were experimentally and theoretically studied. The measurements of fluorescence lifetimes and transient absorption spectra indicated that the planarized triphenylboranes adopt two local minimum structures in the lowest-energy excited singlet (S1) state. The TD-DFT potential energy surface of the S1 state possesses at least two minimum energy structures associated with a planar and a bowl-shaped molecular structure. The theoretical S1–S0 transition energies at these geometries were in good agreement with the experimentally observed values. These results indicated that the plane-to-bowl structural relaxation in the S1 state is the origin of the dual fluorescence. Based on the calculated partial atomic charge on the boron atom, the structural deformation to the bowl-shaped structure results in an increase in the electron density on the boron center. Thus, the enhanced intramolecular charge-transfer character plays a role in this structural deformation. Similar behavior was also observed for trigonally π-expanded planarized borane derivatives. These results provide an important implication that structural constraint in a planar fashion is not only a strategy to construct a rigid skeleton, but also a viable mechanism to impart flexibility to the skeleton.

  尽管三苯基硼烷在结构上受到限制，但其平面化的三个亚甲基桥在 340 纳米和 400 纳米附近显示出双重荧光带。为了阐明其原因，我们对它们的激发态动力学进行了实验和理论研究。荧光寿命和瞬态吸收光谱的测量结果表明，平面化三苯基硼烷在能量最低的激发单态（S1）采用了两种局部最小结构。S1 态的 TD-DFT 势能面至少具有两种最低能量结构，分别与平面和碗状分子结构相关。这些几何结构下的 S1-S0 理论转变能与实验观测值非常吻合。这些结果表明，S1 态的平面到碗形结构弛豫是双重荧光的起源。根据计算得出的硼原子上的部分原子电荷，结构变形为碗状结构会导致硼中心的电子密度增加。因此，分子内电荷转移特性的增强在这种结构变形中起了作用。在三棱 π 展开的平面化硼烷衍生物中也观察到了类似的行为。这些结果提供了一个重要的含义，即平面结构限制不仅是构建刚性骨架的一种策略，也是赋予骨架灵活性的一种可行机制。
• Planarized B-phenylborataanthracene anions: structural and electronic impacts of coplanar constraint
  作者：Tomokatsu Kushida、Zhiguo Zhou、Atsushi Wakamiya、Shigehiro Yamaguchi

  DOI：10.1039/c2cc35874c

  日期：——

  Potassium and lithium salts of anionic B-phenylborataanthracenes, whose phenyl groups were fixed in a coplanar fashion, were synthesized. These compounds exhibited solvent-separated ion pair structures both in the crystalline state and in solution. Planarization of the phenyl moiety had a remarkable impact on the photophysical properties, such as the red-shifted absorption and intense fluorescence.

  我们合成了阴离子 B-苯基硼烷蒽的钾盐和锂盐，其苯基以共面方式固定。这些化合物在晶体状态和溶液中都表现出溶剂分离的离子对结构。苯基的平面化对光物理性质有显著影响，如红移吸收和强烈荧光。
• Planarized Triarylboranes: Stabilization by Structural Constraint and Their Plane-to-Bowl Conversion
  作者：Zhiguo Zhou、Atsushi Wakamiya、Tomokatsu Kushida、Shigehiro Yamaguchi

  DOI：10.1021/ja211944q

  日期：2012.3.14

  Triphenylborane and 9,10-diphenyl-9,10-dihydro-9,10-diboraanthracene, constrained to a planar arrangement with methylene tethers, were synthesized by intramolecular multi-fold Friedel-Crafts cyclization. These compounds were stable toward air, water, and amines, despite the absence of steric protection in the vertical direction with respect to the B atoms, and showed characteristic structural, electronic, and photophysical properties. In addition, upon treatment with a fluoride ion, these compounds underwent a plane-to-bowl conversion in a controlled manner.
• JP5959171
  申请人：——

  公开号：——

  公开（公告）日：——