bis(2,4,6-trichlorophenyl)diazomethane | 91693-00-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(2,4,6-trichlorophenyl)diazomethane
• 英文别名: Bis-(2.4.6-trichlor-phenyl)-diazomethan；1,1'-(Diazomethylene)bis(2,4,6-trichlorobenzene)；1,3,5-trichloro-2-[diazo-(2,4,6-trichlorophenyl)methyl]benzene
• CAS: 91693-00-4
• 化学式: C₁₃H₄Cl₆N₂
• 分子量: 400.906
• InChiKey: IRAWIBQJQRAXCS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  21
• 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：
  2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bis(2,4,6-trichlorophenyl)diazomethane 以 苯 为溶剂， 生成 2,2',4,4',6,6'-hexachlorodiphenyl-carbene
  参考文献：
  名称：

  四甲基哌啶N-氧化物与持久性三重态二苯基卡宾的反应。

  摘要：

  已显示具有相当稳定性的持久性三重态二苯基卡宾被四甲基哌啶N-氧化物（TEMPO）捕获，可将相应的二苯甲酮与四甲基哌啶一起作为主要产物，这表明该反应模式与母体三重态二苯基卡宾所观察到的基本相同。通过激光闪光光解技术测量淬灭反应的绝对速率常数，并将其与通过其他典型的三重态卡宾淬灭剂淬灭的绝对速率常数进行比较。结果表明，TEMPOs对三重碳烯的反应性低于氧气，但高于1,4-环己二烯。讨论了TEMPO作为三重碳烯卡宾淬灭剂相对于其他淬灭剂的优势，

  DOI：

  10.1039/b400892h
• 作为产物：
  描述：

  bis(2,4,6-trichloro-phenyl)-methane 在 silver tetrafluoroborate 、 氯 、 过氧化苯甲酰 作用下， 生成 bis(2,4,6-trichlorophenyl)diazomethane
  参考文献：
  名称：

  A Study of Hindered Divalent Carbon Species and Diazo Compounds

  摘要：

  DOI：

  10.1021/ja01065a010

文献信息

• Reaction of tetramethylpiperidine N-oxides with persistent triplet diphenylcarbenes
  作者：Jun-ichi Nakajima、Katsuyuki Hirai、Hideo Tomioka

  DOI：10.1039/b400892h

  日期：——

  triplet diphenylcarbenes with considerable stability have been shown to be trapped by tetramethylpiperidine N-oxides (TEMPOs) to give the corresponding benzophenones as major products along with tetramethylpiperidine, which indicates that the reaction pattern is essentially identical with that observed for parent triplet diphenylcarbene. The absolute rate constants for the quenching reaction were measured

  已显示具有相当稳定性的持久性三重态二苯基卡宾被四甲基哌啶N-氧化物（TEMPO）捕获，可将相应的二苯甲酮与四甲基哌啶一起作为主要产物，这表明该反应模式与母体三重态二苯基卡宾所观察到的基本相同。通过激光闪光光解技术测量淬灭反应的绝对速率常数，并将其与通过其他典型的三重态卡宾淬灭剂淬灭的绝对速率常数进行比较。结果表明，TEMPOs对三重碳烯的反应性低于氧气，但高于1,4-环己二烯。讨论了TEMPO作为三重碳烯卡宾淬灭剂相对于其他淬灭剂的优势，
• An ESR insight into the thermally activated structural relaxation of the bis(2,4,6-trichlorophenyl)carbene in relation to the molecular mobility of the immediate surroundings
  作者：Boris P. Makarov、Hideo Tomioka

  DOI：10.1039/b404061a

  日期：——

  The dark geometrical relaxation of sterically congested diarylcarbenes under matrix conditions was studied by ESR using bis(2,4,6-trichlorophenyl)carbene as a test molecule. The initial decrease of the parameter D has been found to proceed independently from the well-known expansion of the cental carbenic angle. The latter manifested by the reduction of the parameter E appears to be in correlation with the molecular mobility of the immediate surroundings probed by the reorientation of the primarily aligned test carbene. The complicated nature of the geometrical relaxation of the test carbene was interpreted in terms of the competition of the release of the congestion at the carbenic center and the restraints imposed by a matrix cage on any geometrical changes of the guest molecule.

  使用双(2,4,6-三氯苯基)卡宾作为测试分子，通过ESR研究了基质条件下空间拥挤的二芳基卡宾的暗几何弛豫。已发现参数 D 的初始减小与众所周知的中心卡宾角的扩展无关。后者表现为参数 E 的减小，似乎与通过主要对齐的测试卡宾的重新定向探测到的周围环境的分子迁移率相关。测试卡宾几何弛豫的复杂性质可以通过卡宾中心拥塞释放的竞争和基质笼对客体分子的任何几何变化施加的限制来解释。
• Chemistry, kinetics, and spectroscopy of highly hindered diarylcarbenes. The case of decachlorodiphenylcarbene
  作者：Hideo Tomioka、Katsuyuki Hirai、Takehito Nakayama

  DOI：10.1021/ja00057a010

  日期：1993.2

  Bis(pentachlorophenyl)diazomethane (1a) was prepared, and reactivities of perchlorodiphenylcarbene (2a) generated by photolysis of 1a were investigated not only in terms of product analysis but also by using flash photolysis techniques. Although the major reaction found for 2a was dimerization forming perchlorotetraphenylethylene and was essentially similar to that observed for 2,2',4,4',6,6'-hexachlorodiphenylcarbene (2b), product distribution clearly indicated that the carbenic center in 2a is more rigidly protected than that in 2b by the four ortho chloro substituents which are buttressed by the four meta chloro groups. Irradiation of 1a in a 2-methyltetrahydrofuran glass at 77 K resulted in the appearance of the absorption due to triplet 2a at 356, 493, and 525 nm. Flash photolysis of 1a in benzene solution produced a transient absorption due to 2a at 357 nm, which decayed in second order in accordance with the product analysis data. The rate constant for dimerization of 2a was determined to be 2.5 +/- 0.1 x 10(6) M-1 s-1, 3 orders of magnitude smaller than that of unsubstituted diphenylcarbene. The triplet carbene (2a) was trapped by oxygen to generate the perchlorobenzophenone oxide showing its maximum at 390 nm (t1/2 = 510 +/- 9 ms) and also by 1,4-cyclohexadiene to produce bis(perchlorophenyl)methyl radical (lambda(max) 376 nm with the rate constant of 6.2 x 10(3) M-1 s-1.
• A Study of Hindered Divalent Carbon Species and Diazo Compounds
  作者：Howard E. Zimmerman、Donald H. Paskovich

  DOI：10.1021/ja01065a010

  日期：1964.6
• Structure Determination of Triplet Diphenylcarbenes by in Situ X-ray Crystallographic Analysis
  作者：Masaki Kawano、Katsuyuki Hirai、Hideo Tomioka、Yuji Ohashi

  DOI：10.1021/ja067306b

  日期：2007.2.1

  terms of the carbene angle is extremely flat and changes in the angles have little effect on the energies. Triplet DPCs with a sterically congested carbene center are trapped in a structure dictated by the precursor structure in a rigid matrix, even if this is not the thermodynamically most stable geometry, but undergo geometrical relaxation upon softening the matrix to relieve steric compression. ESR

  通过原位 X 射线晶体学、光谱学和理论计算研究了以下二苯基重氮甲烷的晶态光反应：双（2,4,6-三氯苯基）重氮甲烷（1-N2），双（2,4,6-三溴苯基） )重氮甲烷 (2-N2), 双 (2,6-二溴-4-甲基苯基) 重氮甲烷 (3-N2), 双 (2,6-二溴-4-叔丁基苯基) 重氮甲烷 (4-N2), (2 ,4,6-三溴苯基)-(2,6-二甲基-4-叔丁基苯基)重氮甲烷(5-N2)、双(4-溴苯基)重氮甲烷(6-N2)和重氮芴(7-N2)。确定了 1、2 和 4 的光致三重二苯卡宾 (DPC) 的晶体结构。我们发现它们在结晶状态下获得的结构信息与之前在玻璃基质中通过光谱获得的结构信息之间存在显着差异。尽管 1、2、和 4 在溶液中具有显着不同的稳定性，仅观察到它们结构参数的细微差异，除了它们的 C(:)-Ar 键长。值得注意的是，4 (1.374 A) 的 C(:)-Ar 的平均键长明显短于