4a,4b-dihydrophenanthrene | 13020-78-5

• 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: 4a,4b-dihydrophenanthrene
• 英文别名: 4a,4b-Dihydrophenanthren
• CAS: 13020-78-5
• 化学式: C₁₄H₁₂
• 分子量: 180.249
• InChiKey: ZQNQJMXFVWUBDO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• 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：

  4a,4b-dihydrophenanthrene 在 (isomerization) 作用下， 生成 顺式-二苯乙烯
  参考文献：
  名称：

  4a，4b-二氢菲的结构，光谱，光化学和热反应

  摘要：

  对及其衍生物的溶液进行紫外线照射，得到它们各自的顺式和反式异构体的混合物，在许多情况下还包括4a，4b-二氢菲或其相应的衍生物。光环化的程度在很大程度上取决于用于照射的光的波长。在二苯乙烯中的光平稳状态下，通过在280 m µ处照射可获得最大的光环化（21％）。在二苯基环戊烯中，68％的起始化合物经历环化反应成环戊烯二氢菲。环状产物的吸收光谱在三个主要谱带上均相似，分别约为460、310和240 m µ。。这些带的数量，位置和强度可以通过辛普森的exiton方法正确预测。由六甲基sti形成的六甲基二氢菲的纳米光谱和分子量，为4a，4b-二氢菲及其衍生物建议的结构提供了明确的证据。光环化反应是完全可逆的反应，因为母体顺式-lb或其相应的衍生物可以通过热作用或在可见光区域的照射进行重整。详细研究了光化学成环和裂变，以及热裂变，特别是在二苯基环戊烯⇌环戊烯二氢菲体系中，该体系不被顺式-反式复杂互

  DOI：

  10.1039/j29670000662
• 作为产物：
  描述：

  顺式-二苯乙烯 生成 4a,4b-dihydrophenanthrene
  参考文献：
  名称：

  电子对光化学的影响：高度激发的二苯乙烯和偶氮苯的不同反应动力学

  摘要：

  对反式二苯乙烯、顺二苯乙烯和偶氮苯进行的超快时间分辨质谱和结构动力学实验，在激发高电子态的情况下，揭示了丰富多样的光化学反应动力学。发现所有过程都与众所周知的较低电子表面上的光化学完全不同。在反式二苯乙烯中，6 eV 的激发诱导苯基扭转运动，而在顺式二苯乙烯中，它导致超快闭环形成 4a,4b-二氢菲。偶氮苯在超快的时间尺度上解离，而不是像在较低的表面上那样异构化。样品分子的光化学动力学沿着陡峭的势能表面和锥形交叉点进行。因此，动力学比振动弛豫快得多，

  DOI：

  10.1021/ja108598w

文献信息

• Photochemistry of the phenanthrene-stilbene system. Cycloaddition and singlet-sensitized isomerization
  作者：Richard A. Caldwell、Kazuhiko Mizuno、P. E. Hansen、L. P. Vo、M. Frentrup、C. D. Ho

  DOI：10.1021/ja00414a037

  日期：1981.12
• Photochemistry of supramolecular complex formed by trans-stilbene and the metal–organic coordination polymer
  作者：Veronica V. Semionova、Evgeni M. Glebov、Valeri V. Korolev、Sergey A. Sapchenko、Denis G. Samsonenko、Vladimir P. Fedin

  DOI：10.1016/j.ica.2013.09.048

  日期：2014.1

  Supramolecular adduct consisting from the metal-organic framework (MOF) [Zn-4(dmf)(ur)(2)(ndc)(4)] (ndc(2) is 2,6-naphtalenedicarboxylate, ur is urotropin, and dmf is N,N'-dimethylformamide) and trans-stilbene was synthesized and its photochemistry was studied. The quantum yield of trans-cis photoisomerization of stilbene in adduct (0.2) was found to be an order of magnitude higher than for crystalline trans-stilbene and comparable with that in organic solvents. The results demonstrate that the creation of MOFs adducts with organic photochroms is a prospective approach for the creation of new hybrid photochromic materials. (C) 2013 Elsevier B.V. All rights reserved.
• Femtosecond laser studies of the cis-stilbene photoisomerization reactions: the cis-stilbene to dihydrophenanthrene reaction
  作者：Stephen T. Repinec、Roseanne J. Sension、Arpad Z. Szarka、Robin M. Hochstrasser

  DOI：10.1021/j100178a026

  日期：1991.12

  After optical excitation of cis-stilbene, ground-state dihydrophenanthrene (DHP) is formed in 1.7 ps (hexadecane) via kinetically required intermediate(s) present during the first 300 +/- 200 fs. The DHP is formed hot, and its cooling takes place over the time scale of 35 ps. The DHP spectrum in the region around 450 nm is present throughout the time scale studied (200 fs to 50 ms). The angle between the cis and resulting DHP transition dipoles is 38-degrees at the earliest times measured, which significantly deviates from the alignment expected from a one-dimensional reaction coordinate involving rotations of the phenyl rings. It is proposed that the ethylene bond axis rotates significantly during the isomerization to DHP, perhaps as a result of rotation of the whole molecule in the laboratory frame. Experiments with DHP indicate ultrafast (< 500 fs) ring opening leading toward DHP and cis-stilbene ground-state products.
• Femtosecond laser studies of the <i>cis</i>‐stilbene photoisomerization reactions
  作者：Roseanne J. Sension、Stephen T. Repinec、Arpad Z. Szarka、Robin M. Hochstrasser

  DOI：10.1063/1.464824

  日期：1993.4.15

  Femtosecond laser studies have been performed on the photoisomerization reactions of cis-stilbene to obtain the most detailed understanding to date of a polyatomic isomerization reaction in a condensed phase environment. These experiments demonstrate that vibrationally hot product molecules are formed within a few hundred femtoseconds of the escape of the molecule from the cis* region of the potential energy surface. Although the cis to trans reaction may proceed via a twisted intermediate structure, this intermediate is not intercepted on the ∼150 fs time scale. The frictional effects on the cis to trans reaction coordinate are found to be important and account for the anisotropy of the trans product molecules. Specific experiments presented in detail are the absorption spectrum of electronically excited cis molecules (cis*); the anisotropy decays for cis* showing motion along the reaction coordinate; the detection of the trans-stilbene product using transient fluorescence and transient absorption, confirming that the reaction generates hot product states and that the Franck–Condon modes are largely spectators in the reaction; the anisotropy (alignment) of trans product molecules illustrating the effect of friction coupling overall motion to the reaction coordinate; and a theoretical treatment of three-pulse anisotropy experiments.
• <i>Cis</i>‐stilbene isomerization: Temperature dependence and the role of mechanical friction
  作者：David C. Todd、Graham R. Fleming

  DOI：10.1063/1.464672

  日期：1993.1

  The fluorescence decay time of cis-stilbene has been measured in a variety of solvents over a large temperature range. An isoviscosity Arrhenius plot in n-alkanes yields an activation energy of 386±29 cm−1. We interpret this result as an upper limit for the cis-stilbene to trans-stilbene barrier in nonpolar solvents. Isoviscosity plots in small alcohols are nonlinear, indicating complicated behavior in this solvent type. The excited state decay times in n-alcohols and n-alkane solvents correlate well with each other when plotted as a function of chain length, n. We infer from this plot that macroscopic viscosity is a poor measure of the friction felt by the isomerizing species when changing solvent, and that the potential energy surface is not substantially altered between n-alkanes and n-alcohols with n≥5. Decay times measured in 2-propanol at 490, 475, 453, and 440 nm emission differ by no more than 90 fs, indicating that there is little or no spectral evolution during the excited state lifetime. A short component in the fluorescence anisotropy decay of cis-stilbene and a decrease in the excited state lifetime due to deuterium substitution for the ethylenic hydrogens are observed in both polar and nonpolar solvents. Treating DHP formation as a thermally activated process which competes with the cis to trans isomerization, we determine a range of model dependent cis to trans activation energies in alkanes of −300 to +380 cm−1.