反式-1，2二苯乙烯-D12 | 16341-52-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 中文名称: 反式-1，2二苯乙烯-D12
• 英文名称: trans-stilbene-d12
• 英文别名: trans-Stilben；trans-Stilbene-D12；1,2,3,4,5-pentadeuterio-6-[(E)-1,2-dideuterio-2-(2,3,4,5,6-pentadeuteriophenyl)ethenyl]benzene
• CAS: 16341-52-9
• 化学式: C₁₄H₁₂
• 分子量: 192.154
• InChiKey: PJANXHGTPQOBST-KVFDGITRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  反式-1，2二苯乙烯-D12 以 正己烷 为溶剂， 生成 perdeuterio-cis-stilbene
  参考文献：
  名称：

  Unimolecular reactions in isolated and collisional systems: Deuterium isotope effect in the photoisomerization of stilbene

  摘要：

  The isomerization of t-stilbene (stilbene h12 ) and three deuterated derivatives has been studied in a supersonic expansion, the thermal gas phase, and solution. In the jet we find that almost all effect of full deuteration (stilbene d12 ) is produced by deuteration of the two ethylinic hydrogens only (stilbene d2 ). Complete deuteration of the phenyl rings (stilbene d10 ) has rather little influence on the decay of the jet-cooled molecule. Nonexponential decays are found at intermediate excess energies in the jet-cooled system, with the degree of nonexponentiality decreasing with increasing excess energy. The ordering of the decay rates observed in the jet is not consistent with previous RRKM calculations of the isomerization rates of stilbene h12 and d2. Using similar parameters the calculations consistently place the stilbene d2 and stilbene d10 curves in the wrong order. Our results suggest extensive but not complete vibrational relaxation in the isolated molecule. Vibrational redistribution rapidly becomes complete in the presence of buffer gas. In thermal samples the isomerization rates of stilbene h12 and stilbene d10 are identical over a wide range of solvents and temperatures. By contrast the isomerization rates in stilbene d2 and stilbene d12 are 1.4 and 1.5 times slower than in stilbene h12. Again, these ratios appear constant over a wide range of experimental conditions.

  DOI：

  10.1063/1.455342
• 作为产物：
  描述：

  反式-1,2-二苯乙烯 在 五甲基二乙烯三胺 、 sodium 2,2,6,6-tetramethylpiperidide 、 氘代苯 作用下， 生成 反式-1，2二苯乙烯-D12
  参考文献：
  名称：

  超碱性氨基钠供体NaTMP·PMDETA催化氢同位素交换芳烃全氘化

  摘要：

  氢同位素交换 (HIE) 已成为制备氘代分子的研究最多的方法之一，最近主要关注过渡金属的金属催化 C-H 活化。在这里，我们报告了使用简单的氨基钠 NaTMP（TMP = 2,2,6,6-四甲基哌啶）与三齿 Lewis 供体 PMDETA（N，N，N '，N '' ，N '' -五甲基二亚乙基三胺）结合使用能够在温和的反应条件下使用 C 6 D 6催化促进一系列非活化芳烃的 HIE作为氘源。建立 NaTMP 用于芳香分子氘化的潜力，几种非活化底物，如萘、二苯乙炔和二苯乙烯可以在温和的反应条件下被氘化，而不需要过渡金属。将 NMR 研究与关键有机金属中间体的分离相结合，我们证明 NaTMP/PMEDTA 部分金属化 C 6 D 6的能力，同时产生 TMP(D)，是实现催化氘化的关键。

  DOI：

  10.1021/jacs.2c09778

文献信息

• Platinum on Carbon-Catalyzed H-D Exchange Reaction of Aromatic Nuclei due to Isopropyl Alcohol-Mediated Self- Activation of Platinum Metal in Deuterium Oxide
  作者：Yoshinari Sawama、Tsuyoshi Yamada、Yuki Yabe、Kosuke Morita、Kyoshiro Shibata、Masahiro Shigetsura、Yasunari Monguchi、Hironao Sajiki

  DOI：10.1002/adsc.201201102

  日期：2013.5.17

  simple deuteration method of arenes using the platinum on carbon‐isopropyl alcohol‐cyclohexane‐deuterium oxide combination under hydrogen gas‐free conditions was accomplished. Since the hydrogen–deuterium exchange reaction cannot be promoted without isopropyl alcohol, zerovalent platinum metal (on carbon) is self‐activated by the in situ‐generated very low amount of hydrogen or hydrogen–deuterium gas

  实现了一种在无氢气条件下使用碳-异丙醇-环己烷-氧化氘上的铂结合的芳烃高效简单的氘化方法。由于没有异丙醇无法促进氢-氘交换反应，零价铂金属（在碳上）会被原位生成的极少量氢或由异丙醇或异丙醇-d衍生的氢-氘气自行活化。1个。氘标记的具有高氘含量的化合物可以很容易地通过碳上铂的过滤和简单的萃取来分离。从过程化学的角度来看，目前的无氢气方法是安全的，分子中具有各种可还原功能的各种芳烃可以有效，直接地进行氘标记，而不会发生不希望的还原。
• Unimolecular reactions in isolated and collisional systems: Deuterium isotope effect in the photoisomerization of stilbene
  作者：Scott H. Courtney、Michael W. Balk、Laura A. Philips、Steven P. Webb、Ding Yang、Donald H. Levy、Graham R. Fleming

  DOI：10.1063/1.455342

  日期：1988.12

  The isomerization of t-stilbene (stilbene h12 ) and three deuterated derivatives has been studied in a supersonic expansion, the thermal gas phase, and solution. In the jet we find that almost all effect of full deuteration (stilbene d12 ) is produced by deuteration of the two ethylinic hydrogens only (stilbene d2 ). Complete deuteration of the phenyl rings (stilbene d10 ) has rather little influence on the decay of the jet-cooled molecule. Nonexponential decays are found at intermediate excess energies in the jet-cooled system, with the degree of nonexponentiality decreasing with increasing excess energy. The ordering of the decay rates observed in the jet is not consistent with previous RRKM calculations of the isomerization rates of stilbene h12 and d2. Using similar parameters the calculations consistently place the stilbene d2 and stilbene d10 curves in the wrong order. Our results suggest extensive but not complete vibrational relaxation in the isolated molecule. Vibrational redistribution rapidly becomes complete in the presence of buffer gas. In thermal samples the isomerization rates of stilbene h12 and stilbene d10 are identical over a wide range of solvents and temperatures. By contrast the isomerization rates in stilbene d2 and stilbene d12 are 1.4 and 1.5 times slower than in stilbene h12. Again, these ratios appear constant over a wide range of experimental conditions.
• Perdeuteration of Arenes via Hydrogen Isotope Exchange Catalyzed by the Superbasic Sodium Amide Donor Species NaTMP·PMDETA
  作者：Andreu Tortajada、Eva Hevia

  DOI：10.1021/jacs.2c09778

  日期：2022.11.9

  Here we report the use of a simple sodium amide, NaTMP (TMP = 2,2,6,6-tetramethylpiperidide), combined with tridentate Lewis donor PMDETA (N,N,N′,N″,N″-pentamethyldiethylenetriamine), which is able to catalytically promote the HIE of a series nonactivated arenes under mild reaction conditions using C6D6 as the deuterium source. Establishing the potential of NaTMP for the deuteration of aromatic molecules

  氢同位素交换 (HIE) 已成为制备氘代分子的研究最多的方法之一，最近主要关注过渡金属的金属催化 C-H 活化。在这里，我们报告了使用简单的氨基钠 NaTMP（TMP = 2,2,6,6-四甲基哌啶）与三齿 Lewis 供体 PMDETA（N，N，N '，N '' ，N '' -五甲基二亚乙基三胺）结合使用能够在温和的反应条件下使用 C 6 D 6催化促进一系列非活化芳烃的 HIE作为氘源。建立 NaTMP 用于芳香分子氘化的潜力，几种非活化底物，如萘、二苯乙炔和二苯乙烯可以在温和的反应条件下被氘化，而不需要过渡金属。将 NMR 研究与关键有机金属中间体的分离相结合，我们证明 NaTMP/PMEDTA 部分金属化 C 6 D 6的能力，同时产生 TMP(D)，是实现催化氘化的关键。