di-(9-anthryl)diazomethane | 35391-66-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: di-(9-anthryl)diazomethane
• 英文别名: Di(9-anthryl)diazomethane；9,9'-Dianthryldiazomethan；9-[anthracen-9-yl(diazo)methyl]anthracene
• CAS: 35391-66-3
• 化学式: C₂₉H₁₈N₂
• 分子量: 394.475
• InChiKey: DURIBJKIQZQEJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  31
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  di-(9-anthryl)diazomethane 以 苯 为溶剂， 以50%的产率得到Nonadecacyclo[43.6.6.62,9.611,18.619,26.628,35.636,43.03,8.012,17.020,25.029,34.037,42.046,51.052,57.058,63.064,69.070,75.076,81.082,87]heptaoctaconta-3,5,7,9,10,12,14,16,20,22,24,26,27,29,31,33,37,39,41,43,44,46,48,50,52,54,56,58,60,62,64,66,68,70,72,74,76,78,80,82,84,86-dotetracontaene
  参考文献：
  名称：

  Triplet Di(9-anthryl)carbene Undergoes Trimerization

  摘要：

  DOI：

  10.1002/1521-3773(20001002)39:19<3478::aid-anie3478>3.0.co;2-l
• 作为产物：
  描述：

  在 吡啶 、 sodium amide 作用下， 生成 di-(9-anthryl)diazomethane
  参考文献：
  名称：

  Electron paramagnetic resonance of 9,9'-dianthrylmethylene. Linear aromatic ground-state triplet methylene

  摘要：

  DOI：

  10.1021/ja00752a093

文献信息

• Di(9-anthryl)carbene Revisited. Product Analysis and Spectroscopic Studies
  作者：Ken-ichi Yoshida、Eiji Iiba、Yoshinori Nozaki、Katsuyuki Hirai、Yasutake Takahashi、Hideo Tomioka、Cheng-Tung Lin、Peter P. Gaspar

  DOI：10.1246/bcsj.77.1509

  日期：2004.8

  Irradiation (λ > 300 nm) of di(9-anthryl)diazomethane (1) in degassed benzene gave the trimer (3) of dianthrylcarbene (2) as the main product along with a small amount of a tetramer (4). The structures of those oligomers were characterized as caged compounds produced as a result of three- and four-fold coupling at the 10 and 10′ positions of 2. Photolysis of 1 in the presence of oxygen with short wavelength UV light resulted in the formation of di(9-anthryl) ketone (5) and anthraquinone (6), while similar irradiation with a longer wavelength light gave 5 and 9-anthryl 9-anthracenecarboxylate (9), which was found to give 6 upon irradiation with a short wavelength light in the presence of oxygen. On the other hand, the photolysis of 4 gave 3 as the main product, while 3 was almost completely photostable under similar conditions. However, irradiation of both 3 and 4 in the presence of oxygen gave 6. In order to elucidate the reactions observed, we carried out spectroscopic studies (matrix EPR and UV/vis spectroscopies as well as laser flash photolysis) with 1, 3, and 4. These studies revealed that 3 generated a trimer diradical (10) formed as a result of C–C bond cleavage upon irradiation and that 10 reformed 3 almost exclusively, while similar photolysis of 1 and 4 generated the same two transient species, 10 and a dimer diradical. It is proposed that triplet carbene 2 equilibrates with the dimer diradical 2-2 and that the main decay pathway of this mixture is to generate the trimer diradical 10 while dimer diradical 2-2 undergoes coupling to produce the tetramer 4. The structure of the triplet carbene in equilibrium with diradicals is also discussed.

  在脱气苯中对二（9-蒽基）二氮杂环丁烷（1）进行辐照（λ > 300 纳米），得到的主要产物是二（9-蒽基）二三碳烯（2）的三聚体（3）以及少量的四聚体（4）。这些低聚物的结构被定性为在 2 的 10 和 10′ 位置进行三倍和四倍偶联后产生的笼状化合物。在氧气存在的情况下，用短波长紫外光对 1 进行光解，可生成二（9-蒽基）酮（5）和蒽醌（6），而用较长波长的光照射可生成 5 和 9-蒽基 9-蒽羧酸酯（9），在氧气存在的情况下，用短波长光照射可生成 6。另一方面，光解 4 的主要产物是 3，而 3 在类似条件下几乎完全光稳定。不过，在有氧气存在的情况下照射 3 和 4 会产生 6。为了阐明所观察到的反应，我们对 1、3 和 4 进行了光谱研究（矩阵 EPR 和 UV/vis 光谱以及激光闪烁光解）。这些研究表明，3 在辐照时会产生一个由于 C-C 键裂解而形成的三聚二叉物（10），而且 10 几乎只对 3 进行重整，而 1 和 4 的类似光解也会产生同样的两个瞬态物种，即 10 和一个二聚二叉物。据推测，三重碳烯 2 与二聚二叉体 2-2 发生了平衡，这种混合物的主要衰变途径是生成三聚二叉体 10，而二聚二叉体 2-2 则通过耦合生成四聚体 4。此外，还讨论了与二拉呋喃平衡的三重碳烯的结构。
• Spectroscopic studies on effects of triptycyl group on structures and reactivities of triplet arylcarbenes
  作者：Hideo Tomioka、Junichi Nakajima、Hidehiko Mizuno、Eiji Iiba、Katsuyuki Hirai

  DOI：10.1139/cjc-77-5-6-1066

  日期：——

  A series of triplet 9-triptycyl(aryl)carbenes, where aryl groups are phenyl, 1- and 2-naphthyl, and 9-anthryl, is generated by photolysis of the corresponding diazomethanes and observed directly by spectroscopic means. Their structures are characterized by electron spin resonance (ESR) spectroscopy in a 2-methyltetrahydrofuran matrix at 77 K, and the reactivities are investigated by laser flash photolysis

  一系列三线态 9-三苯乙烯基（芳基）卡宾，其中芳基是苯基、1-和 2-萘基以及 9-蒽基，通过相应重氮甲烷的光解产生并通过光谱方法直接观察。它们的结构通过 77 K 下 2-甲基四氢呋喃基质中的电子自旋共振 (ESR) 光谱表征，并且在室温下在脱气苯溶液中通过激光闪光光解研究反应性。将数据与带有一系列取代基（即氢、苯基、萘基和蒽基）的其他芳基卡宾的数据进行比较，揭示了三线态芳基卡宾的结构和反应性之间的有趣关系。
• Di(triptycyl)carbene:  A Fairly Persistent Triplet Dialkylcarbene
  作者：Eiji Iiba、Katsuyuki Hirai、Hideo Tomioka、Yoshinori Yoshioka

  DOI：10.1021/ja027794x

  日期：2002.12.1

  The title carbene was generated and characterized by matrix spectroscopy (ESR and UV/vis) and laser flash photolysis along with theoretical calculations, which revealed interesting effects of triptycyl groups on structure and reactivities of carbenes.

  标题卡宾是通过基质光谱（ESR 和 UV/vis）和激光闪光光解以及理论计算生成和表征的，这揭示了三苯环对卡宾结构和反应性的有趣影响。
• Electron paramagnetic resonance of 9,9'-dianthrylmethylene. Linear aromatic ground-state triplet methylene
  作者：E. Wasserman、V. J. Kuck、W. A. Yager、R. S. Hutton、F. D. Greene、V. P. Abegg、N. M. Weinshenker

  DOI：10.1021/ja00752a093

  日期：1971.11
• Triplet Di(9-anthryl)carbene Undergoes Trimerization
  作者：Yasutake Takahashi、Masaaki Tomura、Ken-ichi Yoshida、Shigeru Murata、Hideo Tomioka

  DOI：10.1002/1521-3773(20001002)39:19<3478::aid-anie3478>3.0.co;2-l

  日期：2000.10.2