tris(2,3,5,6-tetrachlorophenyl)methane | 105633-26-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: tris(2,3,5,6-tetrachlorophenyl)methane
• 英文别名: 1,1',1''-Methanetriyltris(2,3,5,6-tetrachlorobenzene)；3-[bis(2,3,5,6-tetrachlorophenyl)methyl]-1,2,4,5-tetrachlorobenzene
• CAS: 105633-26-9
• 化学式: C₁₉H₄Cl₁₂
• 分子量: 657.677
• InChiKey: YZBVZRFMRURYFR-UHFFFAOYSA-N

物化性质

• 熔点：
  294-295 °C(Solv: hexane (110-54-3))
• 沸点：
  586.7±45.0 °C(Predicted)
• 密度：
  1.748±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.8
• 重原子数：
  31
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 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：

  tris(2,3,5,6-tetrachlorophenyl)methane 在 硫酸 、 三氧化硫 作用下， 反应 120.0h， 以89%的产率得到tris(2,3,5,6-tetrachloro-4-sulfophenyl)methane
  参考文献：
  名称：

  具有选择性氧化能力的新型稳定的水溶性三（4-羟基磺酰基四氯苯基）甲基自由基的合成

  摘要：

  据报道，PTM（全氯三苯甲基）系列的新的稳定有机自由基非常易溶于水。该自由基对电子转移过程敏感，描述了在抗坏血酸，邻苯三酚和邻苯二酚作为还原剂存在下这些反应的选择性。还给出了电子顺磁共振谱和电化学行为。

  DOI：

  10.1016/j.tet.2011.02.069
• 作为产物：
  描述：

  1,2,4,5-四氯苯 在 aluminum (III) chloride 作用下， 以 氯仿 为溶剂， 反应 3.0h， 以12%的产率得到tris(2,3,5,6-tetrachlorophenyl)methane
  参考文献：
  名称：

  Trityl radicals in perfluorocarbon emulsions as stable, sensitive, and biocompatible oximetry probes

  摘要：

  EPR oximetry with the use of trityl radicals can enable sensitive O-2 measurement in biological cells and tissues. However, in vitro cellular and in vivo biological applications are limited by rapid trityl probe degradation or biological clearance and the need to enhance probe O-2 sensitivity. We synthesized novel perfluorocarbon (PFC) emulsions, similar to 200 nm droplet size, containing esterified perchlorinated triphenyl methyl (PTM) radicals dispersed in physiological aqueous buffers. These formulations exhibit excellent EPR signal stability, over 20-fold greater than free PTM probes, with high oxygen sensitivity similar to 17 mG/mmHg enabling pO(2) measurement in aqueous solutions or cell suspensions with sensitivity > 0.5 mmHg. Thus, PFC-PTM probes hold great promise to enable combined O-2 delivery and sensing as needed to restore or enhance tissue oxygenation in disease. (C) 2016 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2016.10.066

文献信息

• Perchlorotrityl radical-fluorophore conjugates as dual fluorescence and EPR probes for superoxide radical anion
  作者：Jinhua Wang、Vinh Dang、Wei Zhao、Dongning Lu、Brian K. Rivera、Frederick A. Villamena、Peng George Wang、Periannan Kuppusamy

  DOI：10.1016/j.bmc.2009.11.034

  日期：2010.1

  superoxide radical anion showed quenching of EPR signal and enhancement of fluorescence emission spectrum. This work presents the first example of a perchlorotrityl-fluorophore conjugate that can potentially be employed as a dual probe for the detection of superoxide under oxidative stress-mediated conditions in biological systems.

  合成并表征了全氯三苯甲基自由基，使用不同链长的酰胺接头被荧光团单取代。电子顺磁共振 (EPR) 光谱研究表明自由电子与芳族氢核耦合，并与连接基团的亚甲基氢进行长程耦合。荧光团缀合的三苯甲基与超氧自由基阴离子的反应性表明 EPR 信号淬灭和荧光发射光谱增强。这项工作展示了全氯三苯甲基-荧光团缀合物的第一个例子，它有可能用作双探针，用于在生物系统中氧化应激介导的条件下检测超氧化物。
• An Easy, High-yield Synthesis of Highly Chlorinated Mono-, Di- and Triarylmethanes
  作者：Manuel Ballester、Juan Riera、Juan Castañer、Concepción Rovira、Olag Armet

  DOI：10.1055/s-1986-31479

  日期：——

  A simple, direct, high-yield Friedel-Crafts synthesis of highly chlorinated, overcrowded αH-aryl, αH-diaryl, and αH-triarylmethanes is described. The latter compounds are most valuable chemical precursors of inert free radicals, which are frequently obtained through otherwise cumbersome, medium-to-low-yield aromatic chlorination of triphenylmethane derivatives. The condensation is performed with aluminium chloride at temperatures ranging from 70 to 160°C. The substrate is a benzene with all its hydrogens flanked by two ortho chlorines. The alkylating component is chloroform, αH-heptachlorotoluene (2a) or αH-undecachlorodiphenylmethane (3a). For comparison, the condensation with a few non-sterically-hindered substrates has also been performed.

  描述了一种简单、直接、高产率的Friedel-Crafts合成反应，用于合成高度氯化的拥挤型αH-芳基、αH-二芳基和αH-三芳基甲烷。这些化合物是惰性自由基的最有价值的化学前体，通常通过繁琐的中到低产率的芳香氯化三苯甲烷衍生物获得。该缩合反应在70至160°C的温度下使用氯化铝进行。底物是一个苯环，其所有氢原子旁边都有两个邻位氯原子。烷基化组分为氯仿、αH-七氯甲苯（2a）或αH-十氯二苯甲烷（3a）。为了进行比较，也对一些非立体障碍底物进行了缩合反应。
• Chemical Modification toward Long Spin Lifetimes in Organic Conjugated Radicals
  作者：Ya-Zhong Dai、Bo-Wei Dong、Yi Kao、Zi-Yuan Wang、Hio-Ieng Un、Zheng Liu、Zhi-Jun Lin、Liang Li、Fang-Bai Xie、Yang Lu、Mei-Xing Xu、Ting Lei、Yu-Jie Sun、Jie-Yu Wang、Song Gao、Shang-Da Jiang、Jian Pei

  DOI：10.1002/cphc.201800742

  日期：2018.11.19

  for quantum information processing. However, reports on the spin relaxation mechanisms of organic conjugated molecules are rare and the research methods are also limited. Herein, we study the molecular design and spin relaxation mechanisms by systematically varying the structure of a conjugated radical. We found that solid‐state relaxation times of organic materials are largely different from that in

  用于基于自旋的器件的有机半导体需要较长的自旋弛豫时间。了解它们的自旋弛豫机制对于有机自旋电子器件及其在量子信息处理中的应用至关重要。但是，关于有机共轭分子自旋弛豫机理的报道很少，研究方法也很有限。在本文中，我们通过系统地改变共轭基团的结构来研究分子设计和自旋弛豫机理。我们发现有机材料的固态弛豫时间与溶液状态的弛豫时间有很大不同。我们证明了在三苯基甲基（TM）自由基的芳基环的对位上取代较低的旋磁比核（例如D，Cl）可以显着改善其相干时间（T m）。基于此类自由基的柔性薄膜在环境条件下的超长自旋晶格弛豫时间（T 1）高达35.6（6）μs，T m高达1.08（4）μs，是薄膜中最长的值。更重要的是，使用TM自由基衍生物（5CM），我们首次观察到了薄膜中的室温量子相干性和Rabi循环，这表明有机共轭自由基对于基于自旋的信息处理具有巨大的潜力。
• A Self‐Assembled Homochiral Radical Cage with Paramagnetic Behaviors
  作者：Tianyu Jiao、Hang Qu、Lu Tong、Xiaoyu Cao、Hao Li

  DOI：10.1002/anie.202100655

  日期：2021.4.26

  hyl (PTM) radical trisaldehyde with tris(2‐aminoethyl)amine (TREN) yields a [4+4] tetrahedral radical cage as a racemic pair of homochiral enantiomers in 75 % isolated yield. The structure was characterized by X‐ray crystallography, confirming the homochirality of each cage framework. The homochirality results from intramolecular [CH⋅⋅⋅π] and hydrogen‐bonding interactions within the cage framework

  固有的C 3对称的聚氯三苯甲基（PTM）自由基三醛与三（2-氨基乙基）胺（TREN）的缩合产生[4 + 4]四面体自由基笼，是外消旋的同手性对映异构体对，分离产率为75％。该结构通过X射线晶体学表征，证实了每个笼状骨架的同质性。同质性是由笼内骨架内的分子内[CH⋅⋅⋅π]和氢键相互作用产生的。笼子中的四个PTM自由基经历了弱的空间耦合。磁测量表明，每个笼子具有3.58个自旋。
• A Pure‐Red Doublet Emission with 90 % Quantum Yield: Stable, Colorless, Iodinated Triphenylmethane Solid
  作者：Cheng‐Hao Liu、Ehsan Hamzehpoor、Yoko Sakai‐Otsuka、Thaksen Jadhav、Dmitrii F. Perepichka

  DOI：10.1002/anie.202009867

  日期：2020.12.14

  Red luminescence is found in off‐white tris(iodoperchlorophenyl)methane (3I‐PTMH) crystals which is characterized by a high photoluminescence quantum yield (PLQY 91 %) and color purity (CIE coordinates 0.66, 0.34). The emission originates from the doublet excited state of the neutral radical 3I‐PTMR, which is spontaneously formed and becomes embedded in the 3I‐PTMH matrix. The radical defect can also

  在灰白色的三（碘氯氯苯基）甲烷（3I-PTM H）晶体中发现红色发光，其特征在于高的光致发光量子产率（PLQY 91％）和色纯度（CIE坐标0.66，0.34）。发射源于中性自由基3I-PTM R的双重激发态，它自发形成并嵌入3I-PTM H基质中。根本缺陷也可以故意引入3I-PTM H中保持高PLQY且自由基浓度高达4％的晶体。固定的碘化自由基显示出优异的光稳定性（在连续照射下估计半衰期> 1年）和令人着迷的发光寿命（69 ns）。TD-DFT计算表明，给电子的碘原子加速了辐射跃迁，而刚性的卤素键合基体抑制了非辐射衰变。