2,7-dibromo-trans-10b,10c-dimethyl-10b,10c-dihydropyrene | 13979-83-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 2,7-dibromo-trans-10b,10c-dimethyl-10b,10c-dihydropyrene
• 英文别名: 2,7-dibromo-trans-10b,10c-dimethyldihydropyrene；2,7-Dibrom-trans-15,16-Dimethyl-dihydropyren
• CAS: 13979-83-4
• 化学式: C₁₈H₁₄Br₂
• 分子量: 390.117
• InChiKey: KXACHGNYNYNJSP-IYARVYRRSA-N

物化性质

• 沸点：
  522.0±50.0 °C(Predicted)
• 密度：
  1.69±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.87
• 重原子数：
  20.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  2,7-dibromo-trans-10b,10c-dimethyl-10b,10c-dihydropyrene 在 sodium hydroxide 、 titanium(III) chloride 、 氧气 作用下， 以 四氢呋喃 、 盐酸 、 甲醇 为溶剂， 反应 1.0h， 生成 10b,10c-dimethylpyrene
  参考文献：
  名称：

  使用三氯化钛水溶液的新型Birch还原芳香族化合物：反式-10b，10c-二甲基-2,7,10b，10c-四氢py的阴离子

  摘要：

  的伯奇还原10B，10C二甲基10B，10C-二氢芘的1和蒽可能他们的还原电位的基础上被预测，并用三氯化钛水溶液在接近定量的产率容易地实现。在这些条件下，可以保持芳香烃完好无损地控制硝基还原。从还原获得的己烷得到的阴离子1提供的合成路线的衍生物1从直接取代反应难以接近1。阴离子的氧化二聚导致形成了一系列有趣的产物。

  DOI：

  10.1016/s0040-4039(02)02785-5
• 作为产物：
  描述：

  2,7-Diacethoxy-trans-16,16-dimethyl-15,16-dihydro-pyren 在 N-溴代丁二酰亚胺(NBS) 、 过氧化苯甲酰 作用下， 生成 2,7-dibromo-trans-10b,10c-dimethyl-10b,10c-dihydropyrene
  参考文献：
  名称：

  Aromatic Molecules Bearing Substituents within the Cavity of the π-Electron Cloud. Chemical Properties of trans-15,16-Dimethyldihydropyrene

  摘要：

  DOI：

  10.1021/ja00983a029

文献信息

• Bond Fixation in a [14]Annulene:  Synthesis, Characterization, and ab Initio Computations of Furan Adducts of Dimethyldihydropyrene
  作者：Reginald H. Mitchell、Yongsheng Chen、Vivekanantan S. Iyer、Danny Y. K. Lau、Kim K. Baldridge、Jay S. Siegel

  DOI：10.1021/ja953795w

  日期：1996.1.1

  dimethyldihydropyrene are prepared in order to test the postulate that bicyclic annelations are generally effective at inducing bond localization in aromatic systems. A large 2-ppm down-field shift of the 1H NMR shifts of the internal methyl signals in 15 compared to 16 provides a significant indicator of bond localization in 15. X-ray diffraction analysis of 13 displays regular bond length alternation. Ab initio

  制备二甲基二氢芘的呋喃加合物 13、15 和 16 以测试双环退火通常有效诱导芳香系统中键定位的假设。与 16 相比，15 中内部甲基信号的 1H NMR 位移的大 2 ppm 向下场位移提供了 15 中键定位的重要指标。 13 的 X 射线衍射分析显示规则的键长交替。发现不包括动态电子相关性的从头算计算不足以模拟 1 的分子结构。密度泛函理论很好地模拟 1 并预测与观察到的 NMR 光谱和 X 射线衍射结果一致的 1 衍生物中的键定位。
• Generation of the First Series of Oxonium−Annulenium Dications from <i>trans</i>-15,16-Dimethyldihydropyrene DMDHP:  A Diatropic → Paratropic → Diatropic/Paratropic Manifold by Mono- and Diprotonation
  作者：Kenneth K. Laali、Mutsuo Tanaka、Reginald H. Mitchell、Danny Y. K. Lau

  DOI：10.1021/jo972324k

  日期：1998.5.1

  The 2-formyl derivative of trans-dimethyldihydropyrene DMDHP 5 is monoprotonated with FSO3H/SO2ClF and diprotonated with FSO3H . SbF5 (4:1)/SO2ClF to form persistent carboxonium monocation 5H(+) and carboxonium-annulenium dication 5H(2)(2+), respectively. With the cyclohexenone-fused 8 and cyclopentenone-fused 9 derivatives, the tendency to diprotonate increases, whereby dications 8H(2)(2+) and 9H(2)(2+) are cleanly generated in FSO3H/SO2ClF. However, the monocation 8H(+) could be produced in HOAc . TFAH/CD2Cl2 under exchanging conditions. For 9, diprotonation competes even at these low acidities; the isomeric 10 behaved similarly. The biscyclopentenone-fused derivatives 11 and 12 form bisoxonium ions in TFAH/CD2Cl2 and Lewis acid complexes with SnCl4. The transoid form has a stronger tendency to exist in equilibrium with ring protonation. The charge delocalization pathway in the annulene ring are deduced in the cations and compared with the previously studied ring protonated 12-annulenium ions derived from parent 1 and its a-nitro and 2-bromo derivatives. Examination of the shielding/deshielding trends in the internal methyl protons and the annulene ring protons is used to shed light on the ring current effects in the mono-and dications. The charge delocalization mode at the periphery of the annulenium cation is also evaluated on the basis of magnitude of Delta delta(13)C values. AM1 calculations were used to obtain the relative protonation energies for various sites for comparison with the experiment. Diprotonation of the 2,7-dinitro derivative 13 and oxidation of parent 1 were also examined.