trans-10b,10c-Dimethyl-2-nitro-10b,10c-dihydro-pyren | 13979-82-3

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物
• 英文名称: trans-10b,10c-Dimethyl-2-nitro-10b,10c-dihydro-pyren
• 英文别名: 2-Nitro-trans-15,16-Dimethyl-dihydropyren
• CAS: 13979-82-3
• 化学式: C₁₈H₁₅NO₂
• 分子量: 277.323
• InChiKey: UCKSFHLYSRDMBQ-IYARVYRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.03
• 重原子数：
  21.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  43.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  trans-10b,10c-Dimethyl-2-nitro-10b,10c-dihydro-pyren 在 乙酸酐 、 copper(II) nitrate 作用下， 以 氯仿 为溶剂， 反应 16.0h， 以32%的产率得到2,7-dinitro-trans-10b,10c-dimethyldihydropyrene
  参考文献：
  名称：

  Generation of the First Series of Oxonium−Annulenium Dications from trans-15,16-Dimethyldihydropyrene DMDHP:  A Diatropic → Paratropic → Diatropic/Paratropic Manifold by Mono- and Diprotonation

  摘要：

  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.

  DOI：

  10.1021/jo972324k
• 作为产物：
  描述：

  2-甲基异邻苯二甲醛 在 硫酸氢铵 、 sodium tetrahydroborate 、 硫酸 、 氢溴酸 、 硝酸 作用下， 以 四氢呋喃 、 溶剂黄146 为溶剂， 生成 trans-10b,10c-Dimethyl-2-nitro-10b,10c-dihydro-pyren
  参考文献：
  名称：

  Chemical behavior of cis-15,16-dimethyldihydropyrene

  摘要：

  DOI：

  10.1021/jo00412a011

文献信息

• Über die phototropie des trans-15,16-dimethyldihydropyrens und seiner derivate
  作者：H.-R. Blattmann、W. Schmidt

  DOI：10.1016/0040-4020(70)80025-4

  日期：——

  On irradiation with visible light, trans-15,16-dimethyldihydropyrene (DMDHP) is converted to 15,16-dimethyl[2.2]metacyclophane-4,9-diene (P(DMDHP)). In the dark, P(DMDHP) reverts back to DMDHP in a first order thermal reaction. All the substituted DMDHP-derivatives investigated show this reversible valence tautomerism. From the experimental facts it can be assumed that the photoreaction of the DMDHP

  在可见光照射下，反式-15,16-二甲基二氢py（DMDHP）被转化为15,16-二甲基[2.2]元环烷-4,9-二烯（P（DMDHP））。在黑暗中，P（DMDHP）在一级热反应中还原为DMDHP。研究的所有取代的DMDHP衍生物均显示出这种可逆的价位互变异构现象。根据实验事实，可以假设DMDHP衍生物的光反应仅通过单重态进行。Robinson和Frosch 21理论解释了取代基对光反应量子产率的影响。关于无辐射衰减的速率。结果表明，只有共轭效应才能解释暗反应速率P（DMDHP衍生物）→DMDHP衍生物的差异。在地层的自由焓差，ΔG ˚F 298（DMDHP）°，DMDHP和P之间被确定为2·5千卡/摩尔。
• Aromatic Molecules Bearing Substituents within the Cavity of the π-Electron Cloud. Chemical Properties of <i>trans</i>-15,16-Dimethyldihydropyrene
  作者：J. B. Phillips、R. J. Molyneux、E. Sturm、V. Boekelheide

  DOI：10.1021/ja00983a029

  日期：1967.3