anti-8,16-dimethylacenaphthyleno[1,2-a][2,3]metacyclophan-1-ene | 186977-51-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 吖萘类
• 英文名称: anti-8,16-dimethylacenaphthyleno[1,2-a][2,3]metacyclophan-1-ene
• 英文别名: 25,26-Dimethylhexacyclo[14.7.1.13,7.110,14.02,15.020,24]hexacosa-1(23),2(15),3,5,7(26),10(25),11,13,16,18,20(24),21-dodecaene
• CAS: 186977-51-5
• 化学式: C₂₈H₂₂
• 分子量: 358.483
• InChiKey: HXDXOVXJQMNXRO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  28
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  anti-8,16-dimethylacenaphthyleno[1,2-a][2,3]metacyclophan-1-ene 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 环己烷 为溶剂， 反应 10.0h， 以2%的产率得到trans-2-chloro-10b,10c-dimethylacenaphthyleno[1,2-e]-10b,10c-dihydropyrene
  参考文献：
  名称：

  Synthesis and Diatropicity of trans-10b,10c-Dimethylacenaphthyleno[1,2:e]-10b,10c-dihydropyrene:  A Model Aromatic Molecule To Verify the Effect of Conjugation on the Diatropicity of an Annulene

  摘要：

  The title compound 11 was synthesized from acenaphthenequinone in 11 steps with an overall yield of ca. 1.3%. Photochemical desulfurization of the thiacyclophanene 24 afforded the cyclophanene 28. Photochemical isomerization of 28 to the tetrahydropyrene derivative 32 followed by DDQ oxidation gave the desired dihydropyrene 11. Compound 11 is found to sustain only about 85% of the ring current of the parent dihydropyrene 1. On the basis of our results, a significant effect on the diatropicity of the 14 pi annulene in 11 due to its conjugation with a naphthalene moiety is verified. A correlation between theoretically calculated bond orders and experimentally observed coupling constants for selected bonds in 11 indicates that the inductive effect, relative to the resonance effect, plays a major role in the net effect of conjugation observed in 11. Among several derivatives of dihydropyrene 1, a linear relationship is observed for an empirical correlation between the methyl chemical shifts and the corresponding Dewar resonance energies associated with the benzenoid systems in conjugation with 1. This may serve as a method to estimate the resonance energies of other aromatic systems relative to that of benzene. Compound 11 underwent. electrophilic nitration, acetylation, and bromination readily under mild conditions. The electrophiles reacted selectively with the dihydropyrene system in 11 and not the acenaphthylene moiety in conjugation.

  DOI：

  10.1021/jo961237+
• 作为产物：
  描述：

  2,6-二氯甲苯 在 sodium sulfide 、 lithium aluminium tetrahydride 、 硫酸 、 碘 、 magnesium 、 溶剂黄146 、 1,2-二溴乙烷 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 乙醇 、 环己烷 、 溶剂黄146 为溶剂， 反应 56.75h， 生成 anti-8,16-dimethylacenaphthyleno[1,2-a][2,3]metacyclophan-1-ene
  参考文献：
  名称：

  Synthesis and Diatropicity of trans-10b,10c-Dimethylacenaphthyleno[1,2:e]-10b,10c-dihydropyrene:  A Model Aromatic Molecule To Verify the Effect of Conjugation on the Diatropicity of an Annulene

  摘要：

  The title compound 11 was synthesized from acenaphthenequinone in 11 steps with an overall yield of ca. 1.3%. Photochemical desulfurization of the thiacyclophanene 24 afforded the cyclophanene 28. Photochemical isomerization of 28 to the tetrahydropyrene derivative 32 followed by DDQ oxidation gave the desired dihydropyrene 11. Compound 11 is found to sustain only about 85% of the ring current of the parent dihydropyrene 1. On the basis of our results, a significant effect on the diatropicity of the 14 pi annulene in 11 due to its conjugation with a naphthalene moiety is verified. A correlation between theoretically calculated bond orders and experimentally observed coupling constants for selected bonds in 11 indicates that the inductive effect, relative to the resonance effect, plays a major role in the net effect of conjugation observed in 11. Among several derivatives of dihydropyrene 1, a linear relationship is observed for an empirical correlation between the methyl chemical shifts and the corresponding Dewar resonance energies associated with the benzenoid systems in conjugation with 1. This may serve as a method to estimate the resonance energies of other aromatic systems relative to that of benzene. Compound 11 underwent. electrophilic nitration, acetylation, and bromination readily under mild conditions. The electrophiles reacted selectively with the dihydropyrene system in 11 and not the acenaphthylene moiety in conjugation.

  DOI：

  10.1021/jo961237+

文献信息

• Formation of an aromatic indenide anion in a bridge-annelated [2.2]metacyclophanene: a novel and stereoselective nucleophilic addition to an acenaphthylene derivative
  作者：Pu Chen、Yee-Hing Lai

  DOI：10.1016/s0040-4039(02)02517-0

  日期：2003.1

  Treatment of the acenaphthyleno-annelated thiacyclophanene 4 with n-butyl lithium followed by quenching with methyl iodide unexpectedly afforded the ring-contracted adduct 6. A similar reaction between cyclophanene 2 and n-butyl lithium gave the adduct 14 indicating indirectly that in the former reaction the nucleophilic addition occurred after the Wittig-rearrangement of 4 to form the cyclophanene 13. The relief of geometric strain in the [2.2]metacyclophanene moiety induced by acenaphthyleno-annelation is believed to be the driving force for the nucleophilic attack. The sulfonium salt 7 prepared by methylation of compound 6 underwent a spontaneous Hofmann-elimination, in the absence of a base, to give the intermediate cyclophanediene 18 which valence isomerized to the near-planar dihydropyrene 9. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Synthesis and Diatropicity of <i>trans</i>-10b,10c-Dimethylacenaphthyleno[1,2:<i>e</i>]-10b,10c-dihydropyrene:  A Model Aromatic Molecule To Verify the Effect of Conjugation on the Diatropicity of an Annulene
  作者：Yee-Hing Lai、Pu Chen、Thomas W. Dingle

  DOI：10.1021/jo961237+

  日期：1997.2.1

  The title compound 11 was synthesized from acenaphthenequinone in 11 steps with an overall yield of ca. 1.3%. Photochemical desulfurization of the thiacyclophanene 24 afforded the cyclophanene 28. Photochemical isomerization of 28 to the tetrahydropyrene derivative 32 followed by DDQ oxidation gave the desired dihydropyrene 11. Compound 11 is found to sustain only about 85% of the ring current of the parent dihydropyrene 1. On the basis of our results, a significant effect on the diatropicity of the 14 pi annulene in 11 due to its conjugation with a naphthalene moiety is verified. A correlation between theoretically calculated bond orders and experimentally observed coupling constants for selected bonds in 11 indicates that the inductive effect, relative to the resonance effect, plays a major role in the net effect of conjugation observed in 11. Among several derivatives of dihydropyrene 1, a linear relationship is observed for an empirical correlation between the methyl chemical shifts and the corresponding Dewar resonance energies associated with the benzenoid systems in conjugation with 1. This may serve as a method to estimate the resonance energies of other aromatic systems relative to that of benzene. Compound 11 underwent. electrophilic nitration, acetylation, and bromination readily under mild conditions. The electrophiles reacted selectively with the dihydropyrene system in 11 and not the acenaphthylene moiety in conjugation.