18,18'-di-n-hexyl[9,9']bi[phenanthro[9,10-b]triphenylenyl] | 1052691-91-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 18,18'-di-n-hexyl[9,9']bi[phenanthro[9,10-b]triphenylenyl]
• 英文别名: 2-Hexyl-17-(17-hexyl-2-heptacyclo[16.12.0.03,16.04,9.010,15.019,24.025,30]triaconta-1(18),2,4,6,8,10,12,14,16,19,21,23,25,27,29-pentadecaenyl)heptacyclo[16.12.0.03,16.04,9.010,15.019,24.025,30]triaconta-1(18),2,4,6,8,10,12,14,16,19,21,23,25,27,29-pentadecaene
• CAS: 1052691-91-4
• 化学式: C₇₂H₅₈
• 分子量: 923.253
• InChiKey: BTDIJQVXPLJTCD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  21.3
• 重原子数：
  72
• 可旋转键数：
  11
• 环数：
  14.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  2,3,5,6,2',3',5',6'-octabromo-4,4'-dihexylbiphenyl 、 (Li(THF)4)2*Zr(2,2'-biphenyldiyl)3 以 甲苯 为溶剂， 反应 24.0h， 以5%的产率得到18,18'-di-n-hexyl[9,9']bi[phenanthro[9,10-b]triphenylenyl]
  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