tris(2-[1-(dimethylamino)ethyl]phenyl)boroxine | 89362-74-3

• 英文名称: tris(2-[1-(dimethylamino)ethyl]phenyl)boroxine
• CAS: 89362-74-3；89297-53-0
• 化学式: C₃₀H₄₂B₃N₃O₃
• 分子量: 525.115
• InChiKey: TVNYIFZUEBRKDT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  tris(2-[1-(dimethylamino)ethyl]phenyl)boroxine 在 LiAlH₄ 作用下， 以 not given 为溶剂， 以81%的产率得到2,2,3-trimethyl-2,3-dihydro-1H-1l4-benzo[c][1,2]azaborol-2-ium
  参考文献：
  名称：

  Generation of reactive borenium ions in the 2,3-benzazaborolidine series

  摘要：

  通过使用三苯甲基盐从 3 中进行氢化物抽取而生成的硼离子 1 是一种非常有效的亲电体，从四氟硼酸盐甚至从四[3,5-双（三氟甲基）苯基]硼酸盐中进行氟化物抽取就证明了这一点。

  DOI：

  10.1039/cc9960002721

文献信息

• Effect of Benzylic Methyl Groups on Kinetic Basicity of Amine Ligand in<i>o</i>-Boron Substituted<i>N,N</i>-Dimethylbenzylamines
  作者：Shinji Toyota、Mitsuhiro Asakura、Tadahiro Futawaka、Michinori Oki

  DOI：10.1246/bcsj.72.1879

  日期：1999.8

  Rates of the dissociation of the intramolecular B–N coordination bond in two series of phenylborane derivatives, the boronate and diethylborane complexes, with –CHMeNMe2 or –CMe2NMe2 group at the o-position were determined by the NMR lineshape analysis or saturation transfer method. The new organoboron compounds were synthesized from the corresponding organolithium compounds with appropriate boron reagents. Comparison of the kinetic data with those of the –CH2NMe2 compounds reveals that the barrier height to the dissociation, namely the kinetic basicity of the amine ligand, is increased as the molecule possesses more methyl groups at the benzylic position for both of the series of boron compounds. The X-ray structure of one of the boronate complexes and the NMR titration measurements of model amines indicate that the basicity of the amine ligand is not affected much by the methyl substitution in the coordinated form. Therefore, the substituent effect on the kinetic basicity is mainly ascribed to the destabilization of the transition state by the geminal dimethyl groups rather than to any inductive or steric effects at the initial state, especially for the –CMe2NMe2 compounds.

  在两类苯基硼烷衍生物中，分别为硼酸盐和二乙基硼烷络合物，位于邻位的–CHMeNMe2或–CMe2NMe2基团的分子内B-N协同键的解离速率通过NMR谱线形状分析或饱和转移法进行了测定。这些新的有机硼化合物是由相应的有机锂化合物与适当的硼试剂合成的。与–CH2NMe2化合物的动力学数据进行比较表明，解离的能量障碍高度，即胺配体的动力学基本性，在这两类硼化合物中，随着分子在苄基位置上拥有更多的甲基而增加。一个硼酸盐络合物的X射线结构以及模型胺的NMR滴定测量表明，胺配体的基本性在协调形式中受甲基取代的影响不大。因此，取代基对动力学基本性的影响主要归因于邻位二甲基基团对过渡态的去稳定化，而不是初始状态下的任何诱导或空间效应，尤其是在–CMe2NMe2化合物中。