2,15-dimethylhexahelicene | 69804-70-2

• 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: 2,15-dimethylhexahelicene
• 英文别名: 2,15-Dimethylhexahelicen
• CAS: 69804-70-2；109376-21-8；109376-27-4
• 化学式: C₂₈H₂₀
• 分子量: 356.467
• InChiKey: XRDQVEZDWIHRDL-UHFFFAOYSA-N

物化性质

• 沸点：
  621.9±25.0 °C(Predicted)
• 密度：
  1.218±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.3
• 重原子数：
  28
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  2,15-dimethylhexahelicene 在 N-溴代丁二酰亚胺(NBS) 、 sodium azide 、 过氧化苯甲酰 作用下， 以 四氯化碳 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 2,15-bis(azidomethyl)hexahelicene
  参考文献：
  名称：

  Assembling Nonplanar Polyaromatic Units by Click Chemistry. Study of Multicorannulene Systems as Host for Fullerenes

  摘要：

  Novel compounds with two or three corannulene subunits have been obtained by click chemistry. These exotic systems were synthesized in high yields using the ethynylcorannulene as common reagent. The synergistic action as receptors for fullerenes of several corannulene blocks has been evaluated. It was found that the three-armed derivatives showed efficient complexation abilities toward C-60. Furthermore, a new compound having two corannulene subunits linked to a hexahelicene scaffold has a remarkable affinity constant. Finally, theoretical calculations have been performed to evaluate the formation of their relative adducts containing a C-60 molecule.

  DOI：

  10.1021/acs.orglett.5b01161
• 作为产物：
  描述：

  2,7-双(溴甲基)萘 在 sodium methylate 作用下， 生成 2,15-dimethylhexahelicene
  参考文献：
  名称：

  甲基取代的六螺旋的热消旋

  摘要：

  已经测量了几种Me-取代的六螺旋酮的外消旋速率。看来位置3、4、13和14的Me组没有任何影响；在位置2和15处效果很小；但是，在C（1）和C（16）处的Me取代导致活化自由能大大增加。根据对数据的分析，提出了在1-甲基和1,16-二甲基己烯（以及可能还有庚和辛烯）的外消旋化过程中最高能量的构型是末端环处于正交位置的构象。

  DOI：

  10.1016/0040-4020(78)88387-2

文献信息

• η⁶-Hexahelicene Complexes of Iridium and Ruthenium: Running along the Helix
  作者：Celedonio M. Álvarez、Héctor Barbero、Luis A. García-Escudero、Jose M. Martín-Alvarez、Cristina Martínez-Pérez、Daniel Miguel

  DOI：10.1021/ic300462z

  日期：2012.8.6

  The first eta(6)-complexes of iridium and ruthenium coordinated to helicenes have been obtained. Hexahelicene (1), 2,15-dimethylhexahelicene (2), and 2,15-dibromohexahelicene (3) react with [Cp*IrCl2](2) and AgBF4 in CD3NO2 to afford quantitatively the complexes [Cp*Ir(eta(6-)1)][BF4](2) (4A), [Cp*Ir(eta(6)-2)][BF4](2) (SA), and [Cp*Ir(eta(6)-3)][BF4](2) (6A), respectively. In all cases, the final thermodynamic products are similar, and they exhibit coordination between the 12 e(-) metal fragment [IrCp*](2+) and the terminal ring of the helicene. Monitoring the reaction by NMR shows formation of intermediates, some of which have been fully characterized in solution. These intermediates exhibit the metal fragment coordinated to the internal rings. We have also synthesized the bimetallic complex [(Cp*Ir)(2)(mu(2)-eta(6):eta(6)-2)][BF4](4) (7), achieving coordination between two units [IrCp*](2+) and the helicene 2. Following an analogous methodology, we have prepared the complex [(eta(6)-cymene)Ru(eta(6)-2)][BF4](2) (8), which has been studied by X-ray diffraction, confirming the preferential binding to the terminal aromatic ring.
• Yamamoto, Koji; Sonobe, Hiroyuki; Matsubara, Hiroshi, Angewandte Chemie, 1996, vol. 108, # 1, p. 69 - 70
  作者：Yamamoto, Koji、Sonobe, Hiroyuki、Matsubara, Hiroshi、Sato, Masaaki、Okamoto, Susumu、Kitaura, Kazuo

  DOI：——

  日期：——
• Sato, Masaaki; Yamamoto, Kazuyuki; Sonobe, Hiroyuki, Journal of the Chemical Society. Perkin Transactions 2 (2001), 1998, # 9, p. 1909 - 1913
  作者：Sato, Masaaki、Yamamoto, Kazuyuki、Sonobe, Hiroyuki、Yano, Koji、Matsubara, Hiroshi、Fujita, Hideo、Sugimoto, Toyonari、Yamamoto, Koji

  DOI：——

  日期：——
• Assembling Nonplanar Polyaromatic Units by Click Chemistry. Study of Multicorannulene Systems as Host for Fullerenes
  作者：Celedonio M. Álvarez、Gabriel Aullón、Héctor Barbero、Luis A. García-Escudero、Cristina Martínez-Pérez、Jose M. Martín-Álvarez、Daniel Miguel

  DOI：10.1021/acs.orglett.5b01161

  日期：2015.6.5

  Novel compounds with two or three corannulene subunits have been obtained by click chemistry. These exotic systems were synthesized in high yields using the ethynylcorannulene as common reagent. The synergistic action as receptors for fullerenes of several corannulene blocks has been evaluated. It was found that the three-armed derivatives showed efficient complexation abilities toward C-60. Furthermore, a new compound having two corannulene subunits linked to a hexahelicene scaffold has a remarkable affinity constant. Finally, theoretical calculations have been performed to evaluate the formation of their relative adducts containing a C-60 molecule.
• The thermal racemization of methyl-substituted hexahelicenes
  作者：J.H. Borkent、W.H. Laarhoven

  DOI：10.1016/0040-4020(78)88387-2

  日期：1978.1

  Rates of racemization of several Me-substituted hexahelicenes have been measured. It appeared that Me groups at the positions 3, 4, 13 and 14 have no influence; at the positions 2 and 15 the effect is small; Me-substitution at C(1) and C(16) leads, however, to a large increase of the free energy of activation. From an analysis of the data the suggestion is made that the conformation of highest energy

  已经测量了几种Me-取代的六螺旋酮的外消旋速率。看来位置3、4、13和14的Me组没有任何影响；在位置2和15处效果很小；但是，在C（1）和C（16）处的Me取代导致活化自由能大大增加。根据对数据的分析，提出了在1-甲基和1,16-二甲基己烯（以及可能还有庚和辛烯）的外消旋化过程中最高能量的构型是末端环处于正交位置的构象。