1-己基-4-(4-己基苯基)苯 | 25432-91-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1-己基-4-(4-己基苯基)苯
• 英文名称: 4,4'-dihexylbiphenyl
• 英文别名: 1-hexyl-4-(4-hexylphenyl)benzene
• CAS: 25432-91-1
• 化学式: C₂₄H₃₄
• 分子量: 322.534
• InChiKey: MYTZOPCHPFXFFG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  24
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  1-己基-4-(4-己基苯基)苯 在 溴 、 铁粉 作用下， 以54%的产率得到2,3,5,6,2',3',5',6'-octabromo-4,4'-dihexylbiphenyl
  参考文献：
  名称：

  18,18′-Dihexyl[9,9′]biphenanthro[9,10-b]triphenylene: Construction and Consequences of a Profoundly Hindered Aryl−Aryl Single Bond

  摘要：

  The title compound, 1-Hex, was synthesized by the Zr-mediated biphenylation of 4,4'-dihexyloctabromobiphenyi using (Li(THF)(4))(2)center dot Zr(biphe)(3), where biphe is the 2,2'-biphenyldiyl ligand, in 5% isolated yield. Two independent X-ray diffraction analyses revealed that arene 1-Hex possesses a highly strained and hindered aryl-aryl single bond. This bond causes the phenanthro[9,10-b]triphenylene (PTP) moieties to twist (anthracene subunit dihedral, 69 degrees); the interlocked, helical, homochiral PTP moieties give rise to effective D-2 symmetry. The calculated adiabatic homolytic bond dissociation energy of this strained bond is only 67 kcal/mol, but nonetheless the bond exhibits a surprisingly normal length (1.49 angstrom); the reason is elongation only slowly releases strain. Variable temperature NMR revealed two dynamic processes: hexyl rotation (12.0 +/- 0.4 kcal/mol) and inversion of chirality (15.2 +/- 0.6 kcal/mol). DFT calculations provide rate-determining transitions states, whose energies agree with measured values, and provide insight to the mechanism of these processes. Rotation about the central bond is not involved in either observed process. Calculations demonstrate that rotation does not involve a simple torsion of the equilibrium structure, but rather a complex movement with a barrier of 49 kcal/mol from a slipped-parallel, C-2h intermediate.

  DOI：

  10.1021/ja803396n
• 作为产物：
  描述：

  1-(4-溴苯基)己烷 在 双(乙腈)氯化钯(II) 、 2-[(methylsulfanyl)methyl]-4-phenyl-2H-1,2,3-triazole 、 potassium tert-butylate 、 联硼酸频那醇酯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以91 %的产率得到1-己基-4-(4-己基苯基)苯
  参考文献：
  名称：

  N,S-螯合三唑硫醚钯一锅法合成联芳基化合物

  摘要：

  在这项工作中，对于芳基卤化物与双（频哪醇）二硼的一锅两步偶联反应，我们首先应用了无磷的 N,S-螯合三唑硫化物钯催化体系。同时，我们还进行了细致的配体设计，探索配位硫原子周围环境对反应的影响。实验表明，N 2 -硫醚取代的1,2,3-三唑钯是一种最佳的催化剂。仅需1 mol%的催化剂，反应4 h即可达到定量收率。此外，在该催化体系下，一些低活性的芳基氯化物也可以与双（频哪醇）二硼偶联。我们能够以良好至优异的产率获得含有各种官能团的联芳基化合物。

  DOI：

  10.1071/ch22116

文献信息

• Bumagin, N. A.; Luzikova, E. V.; Beletskaya, I. P., Russian Journal of Organic Chemistry, 1995, vol. 31, # 11, p. 1487 - 1491
  作者：Bumagin, N. A.、Luzikova, E. V.、Beletskaya, I. P.

  DOI：——

  日期：——
• 18,18′-Dihexyl[9,9′]biphenanthro[9,10-<i>b</i>]triphenylene: Construction and Consequences of a Profoundly Hindered Aryl−Aryl Single Bond
  作者：Cameron L. Hilton、Jeremy M. Crowfoot、Pawel Rempala、Benjamin T. King

  DOI：10.1021/ja803396n

  日期：2008.10.8

  The title compound, 1-Hex, was synthesized by the Zr-mediated biphenylation of 4,4'-dihexyloctabromobiphenyi using (Li(THF)(4))(2)center dot Zr(biphe)(3), where biphe is the 2,2'-biphenyldiyl ligand, in 5% isolated yield. Two independent X-ray diffraction analyses revealed that arene 1-Hex possesses a highly strained and hindered aryl-aryl single bond. This bond causes the phenanthro[9,10-b]triphenylene (PTP) moieties to twist (anthracene subunit dihedral, 69 degrees); the interlocked, helical, homochiral PTP moieties give rise to effective D-2 symmetry. The calculated adiabatic homolytic bond dissociation energy of this strained bond is only 67 kcal/mol, but nonetheless the bond exhibits a surprisingly normal length (1.49 angstrom); the reason is elongation only slowly releases strain. Variable temperature NMR revealed two dynamic processes: hexyl rotation (12.0 +/- 0.4 kcal/mol) and inversion of chirality (15.2 +/- 0.6 kcal/mol). DFT calculations provide rate-determining transitions states, whose energies agree with measured values, and provide insight to the mechanism of these processes. Rotation about the central bond is not involved in either observed process. Calculations demonstrate that rotation does not involve a simple torsion of the equilibrium structure, but rather a complex movement with a barrier of 49 kcal/mol from a slipped-parallel, C-2h intermediate.
• N,S-Chelating triazole-thioether palladium for the one-pot synthesis of biaryls
  作者：Qiong Yan、Heng Huang、Xiang Si

  DOI：10.1071/ch22116

  日期：——

  In this work, for the one-pot two-step coupling reaction of aryl halides with bis(pinacol)diboron, we first applied a phosphorus-free N,S-chelated triazole sulfide palladium-catalyzed system. At the same time, we also carried out careful ligand design to explore the effect of the environment around the coordinating sulfur atom on the reaction. Experiments have shown that the N2-thioether substituted

  在这项工作中，对于芳基卤化物与双（频哪醇）二硼的一锅两步偶联反应，我们首先应用了无磷的 N,S-螯合三唑硫化物钯催化体系。同时，我们还进行了细致的配体设计，探索配位硫原子周围环境对反应的影响。实验表明，N 2 -硫醚取代的1,2,3-三唑钯是一种最佳的催化剂。仅需1 mol%的催化剂，反应4 h即可达到定量收率。此外，在该催化体系下，一些低活性的芳基氯化物也可以与双（频哪醇）二硼偶联。我们能够以良好至优异的产率获得含有各种官能团的联芳基化合物。