3-[4’-(diethylboryl)phenyl]pyridine | 247214-56-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 3-[4’-(diethylboryl)phenyl]pyridine
• 英文别名: 3-[4'-(diethylboryl)phenyl]pyridine；Diethyl-(4-pyridin-3-ylphenyl)borane
• CAS: 247214-56-8
• 化学式: C₁₅H₁₈BN
• 分子量: 223.126
• InChiKey: NJIPTNJUZVYRRT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.49
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  溴苯 、 3-[4’-(diethylboryl)phenyl]pyridine 在 四(三苯基膦)钯 氢氧化钾 、 四丁基溴化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以80.5%的产率得到3-([1,1'-biphenyl]-4-yl)pyridine
  参考文献：
  名称：

  Self-Assembly of 3-[4‘-(Diethylboryl)phenyl]pyridine and 3-[3‘-(Diethylboryl)phenyl]pyridine:  Synthesis, Structural Features, and Stability in Solution

  摘要：

  The self-assembly of 3-[4'-(diethylboryl)phenyl]pyridine (3) and 3-[3'-(diethylboryl)phenyl]pyridine (4) was investigated by H-1 and B-11 NMR spectroscopies and vapor pressure osmometry. It can be seen that in solution 3 affords an equilibrium mixture of oligomers including a cyclic trimer as a major component via intermolecular boron-nitrogen coordination bonds, which is supported by temperature-, concentration-, and solvent-dependent behaviors of 3. In contrast, 4 seems to afford a mixture of oligomers including a cyclic dimer in solution. Judging from the low coalescence temperature in variable-temperature NMR in toluene-d(8) and easy scrambling with the corresponding 3-[(diethylboryl)pheny]-5-methoxypyridines at ambient temperature, it is concluded that the intermolecular boron-nitrogen coordination bonds made by 3 or 4 are weaker than those formed by 3-(diethylboryl)pyridine (1) or 2-(diethylboryl)-5-methylpyridine (2). Poor thermal stability was supported by electrospray mass spectrometry and structural analyses utilizing a semi-empirical molecular orbital calculation AM1. It is noted that in the assembly of 4 there is a tendency to maintain high tetrahedral character at the boron atom in the complex at the expense of strain energy. Thus, these features of 3 and 4 in solution are in marked contrast to those of 1 and 2.

  DOI：

  10.1021/jo981632v
• 作为产物：
  描述：

  3-(三甲基锡烷基)-吡啶 在 tris-(dibenzylideneacetone)dipalladium(0) copper(l) iodide 、 正丁基锂 、 四甲基乙二胺 、 三苯胂 作用下， 以 乙醚 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成 3-[4’-(diethylboryl)phenyl]pyridine
  参考文献：
  名称：

  Self-Assembly of 3-[4‘-(Diethylboryl)phenyl]pyridine and 3-[3‘-(Diethylboryl)phenyl]pyridine:  Synthesis, Structural Features, and Stability in Solution

  摘要：

  The self-assembly of 3-[4'-(diethylboryl)phenyl]pyridine (3) and 3-[3'-(diethylboryl)phenyl]pyridine (4) was investigated by H-1 and B-11 NMR spectroscopies and vapor pressure osmometry. It can be seen that in solution 3 affords an equilibrium mixture of oligomers including a cyclic trimer as a major component via intermolecular boron-nitrogen coordination bonds, which is supported by temperature-, concentration-, and solvent-dependent behaviors of 3. In contrast, 4 seems to afford a mixture of oligomers including a cyclic dimer in solution. Judging from the low coalescence temperature in variable-temperature NMR in toluene-d(8) and easy scrambling with the corresponding 3-[(diethylboryl)pheny]-5-methoxypyridines at ambient temperature, it is concluded that the intermolecular boron-nitrogen coordination bonds made by 3 or 4 are weaker than those formed by 3-(diethylboryl)pyridine (1) or 2-(diethylboryl)-5-methylpyridine (2). Poor thermal stability was supported by electrospray mass spectrometry and structural analyses utilizing a semi-empirical molecular orbital calculation AM1. It is noted that in the assembly of 4 there is a tendency to maintain high tetrahedral character at the boron atom in the complex at the expense of strain energy. Thus, these features of 3 and 4 in solution are in marked contrast to those of 1 and 2.

  DOI：

  10.1021/jo981632v

文献信息

• 3-[4′-(Diethylboryl)phenyl]pyridine: Exclusive Crystallization of the Cyclic Tetramer
  作者：Shigeharu Wakabayashi、Natsu Sugiyama、Yasuhiro Ohki、Takahito Itoh、Toshikazu Kitagawa

  DOI：10.1002/asia.201801698

  日期：2019.2.15

  spectroscopy of precipitates of compound 1 suggested that precipitation from acetone and toluene each afforded mixtures of the cyclic trimer and the cyclic tetramer, whereas precipitation from benzene exclusively furnished the cyclic tetramer. Therefore, it appeared that crystallization readily shifted the equilibrium towards the cyclic tetramer in benzene. The thermodynamic parameters for the equilibrium between

  3– [4'-（二乙基硼基）苯基]吡啶（1）在丙酮中于0°C时在溶液中以环状三聚体为主要成分的低聚物混合物形成结晶，得到共结晶的环状四聚体与溶剂分子。类似地，化合物1在10°C的甲苯中和在8°C的苯中的溶液分别为环状四聚体提供了甲苯和苯分子的结合，因此表明环状四聚体是次要成分。化合物1沉淀物的13 C CP / MAS NMR光谱提示从丙酮和甲苯中沉淀可分别得到环状三聚体和环状四聚体的混合物，而从苯中沉淀仅可提供环状四聚体。因此，似乎结晶容易使平衡向苯中的环状四聚体移动。根据van't Hoff图确定，[D 6 ]苯中这两种低聚物之间平衡的热力学参数为ΔH °= -8.8 kcal mol -1和ΔS °= -23.7 cal mol -1  K -1，与先前报道的计算和观察结果一致。