tris(8-carboxy-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methanol | 910912-09-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: tris(8-carboxy-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methanol
• 英文别名: 8-[Bis(4-carboxy-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiol-8-yl)-hydroxymethyl]-2,2,6,6-tetramethyl-[1,3]dithiolo[4,5-f][1,3]benzodithiole-4-carboxylic acid
• CAS: 910912-09-3
• 化学式: C₄₀H₄₀O₇S₁₂
• 分子量: 1017.55
• InChiKey: FKBSNMGQHYEPAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.9
• 重原子数：
  59
• 可旋转键数：
  6
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  436
• 氢给体数：
  4
• 氢受体数：
  19

反应信息

• 作为反应物：
  描述：

  tris(8-carboxy-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methanol 在 三氟乙酸 、 tin(ll) chloride 作用下， 以 二氯甲烷 、 四氢呋喃 为溶剂， 反应 5.0h， 以96%的产率得到tris(8-carboxy-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methyl
  参考文献：
  名称：

  三(2,3,5,6-四硫芳基)甲基阳离子亲核猝灭生成三苯甲基自由基及持久性三(4-羧基-2,3,5,6-四硫芳基)甲基自由基的实用便捷大规模合成

  摘要：

  三(2,3,5,6-四硫芳基)甲基阳离子是由相应的三芳基甲醇在强酸存在下产生的，与亲核试剂反应生成三苯甲基自由基，作为碳阳离子单电子还原的产物。根据亲核试剂的性质，唯一的副产物是抗磁性醌甲基化物或不对称单取代三苯甲基自由基。在此，我们报告了芬兰三苯甲基的大规模合成方案，该方案具有总产率高和重现性好的优点。

  DOI：

  10.1002/ejoc.201300176
• 作为产物：
  描述：

  二氧化碳 、 tris(2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methanol 在 四甲基乙二胺 、 正丁基锂 作用下， 以 正己烷 为溶剂， 反应 26.0h， 以64%的产率得到tris(8-carboxy-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methanol
  参考文献：
  名称：

  多功能三苯甲基自旋标签，用于体外和细胞内生物分子的纳米距离测量。

  摘要：

  在细胞内条件下确定生物大分子的结构是一项相关但具有挑战性的任务。电子顺磁共振（EPR）距离测量与定点自旋标记（SDSL）相结合是此工作的重要工具，但通常使用的一氧化氮自旋标记不适用于细胞内测量。相反，三芳基甲基（三苯甲基）基团是高度持久的，表现出长的弛豫时间和窄的光谱宽度。在这里，描述了三苯甲基旋转标记的通用集合的合成及其在细胞色素P450蛋白的体外和细胞内三苯甲基-铁距离测量中的应用。

  DOI：

  10.1002/anie.201609085

文献信息

• Triarylmethanols with Bulky Aryl Groups and the NOESY/EXSY Experimental Observation of a Two-Ring-Flip Mechanism for the Helicity Reversal of Molecular Propellers
  作者：Victor M. Tormyshev、Alexander M. Genaev、Georgy E. Sal'nikov、Olga Yu. Rogozhnikova、Tatiana I. Troitskaya、Dmitry V. Trukhin、Victor I. Mamatyuk、Dmitry S. Fadeev、Howard J. Halpern

  DOI：10.1002/ejoc.201101243

  日期：2012.1

  Triarylmethanols - the direct precursors of persistent trityl radicals - are racemic mixtures of chiral three-bladed molecular propellers. Depending on bulkiness of aryl groups they exhibit various liabilities to interconversion, the half- life time of room temperature racemization varying in a range between 8.4 hours and 1.32 years. NOESY/EXSY experiment performed on two representative models strongly

  三芳基甲醇-持久性三苯甲基自由基的直接前体-是手性三叶分子螺旋桨的外消旋混合物。取决于芳基基团的体积，它们表现出多种相互转化的责任，室温外消旋的半衰期时间在8.4小时至1。32年之间变化。在两个代表性模型上进行的NOESY / EXSY实验强烈支持用于配置互换的双环翻转机制。
• Preparation of Diversely Substituted Triarylmethyl Radicals by the Quenching of Tris(2,3,5,6-tetrathiaaryl)methyl Cations with C-, N-, P-, and S-Nucleophiles
  作者：Victor M. Tormyshev、Olga Yu. Rogozhnikova、Michael K. Bowman、Dmitry V. Trukhin、Tatiana I. Troitskaya、Vladimir G. Vasiliev、Leonid A. Shundrin、Howard J. Halpern

  DOI：10.1002/ejoc.201301161

  日期：2014.1

  C-, N-, P-, and S-nucleophiles reacted with symmetrical tris(2,3,5,6-tetrathiaaryl)methyl cations, generated from the corresponding triarylmethanols by strong acids, to give a variety of asymmetrical monosubstituted persistent triaryl-methyl (TAM) radicals as the major products. The only byproducts were symmetrical TAMs.

  C-、N-、P-和S-亲核试剂与对称的三(2,3,5,6-四硫芳基)甲基阳离子（由相应的三芳基甲醇通过强酸生成）反应，得到各种不对称单取代的持久三芳基-甲基（TAM）自由基为主要产品。唯一的副产物是对称的 TAM。
• A Simple and Convenient Synthesis of a Multifunctional Spin Probe, Phosphonate Derivative of a Persistent Radical of the Triarylmethyl Series
  作者：O. Yu. Rogozhnikova、D. V. Trukhin、N. B. Asanbaeva、V. M. Tormyshev

  DOI：10.1134/s107042802106004x

  日期：2021.6
• Synthesis and Characterization of PEGylated Trityl Radicals: Effect of PEGylation on Physicochemical Properties
  作者：Wenbo Liu、Jiangping Nie、Xiaoli Tan、Huiqiang Liu、Nannan Yu、Guifang Han、Yutian Zhu、Frederick A. Villamena、Yuguang Song、Jay L. Zweier、Yangping Liu

  DOI：10.1021/acs.joc.6b02590

  日期：2017.1.6

  Tetrathiatriarylmethyl (TAM, trityl) radicals have attracted considerable attention as spin probes for biological electron paramagnetic resonance (EPR) spectroscopy and imaging owing to their sharp EPR singlet signals and high biostability. However, their in vivo applications were limited by the short blood circulation lifetimes and strong binding with albumins. Our previous results showed that PEGylation is a feasible method to overcome the issues facing in vivo applications of TAM radicals. In the present study, we synthesized a series of new PEGylated TAM radicals (TTP1, TPP2, TNP1, TNP2, d-TNP1, and d-TNP3) containing various lengths and numbers of mPEG chains. Our results found that the pattern of PEGylation exerts an important effect on physicochemical properties of the resulting TAM radicals. Dendritic PEGylated TAM radicals, TNP1 and TNP2, have higher water solubility and lower susceptibility for self-aggregation than their linear analogues TPP1 and TPP2. Furthermore, dendritic PEGylated TAM radicals exhibit extremely high stability toward various biological oxidoreductants as well as in rat whole blood, liver homogenate, and following in vivo intravenous administration in mice. Importantly, the deuterated derivatives, especially d-TNP3, exhibit excellent properties including the sharp and O-2-sensitive EPR singlet signal, good biocompatibility, and prolonged kinetics with half-life time of >= 10 h in mice. These PEGylated TAM radicals should be suitable for a wide range of applications in in vivo EPR spectroscopy and imaging.
• Versatile Trityl Spin Labels for Nanometer Distance Measurements on Biomolecules In Vitro and within Cells
  作者：J. Jacques Jassoy、Andreas Berndhäuser、Fraser Duthie、Sebastian P. Kühn、Gregor Hagelueken、Olav Schiemann

  DOI：10.1002/anie.201609085

  日期：2017.1.2

  distance measurements in combination with site‐directed spin labeling (SDSL) are a valuable tool in this endeavor but the usually used nitroxide spin labels are not well‐suited for in‐cell measurements. In contrast, triarylmethyl (trityl) radicals are highly persistent, exhibit a long relaxation time and a narrow spectral width. Here, the synthesis of a versatile collection of trityl spin labels and their

  在细胞内条件下确定生物大分子的结构是一项相关但具有挑战性的任务。电子顺磁共振（EPR）距离测量与定点自旋标记（SDSL）相结合是此工作的重要工具，但通常使用的一氧化氮自旋标记不适用于细胞内测量。相反，三芳基甲基（三苯甲基）基团是高度持久的，表现出长的弛豫时间和窄的光谱宽度。在这里，描述了三苯甲基旋转标记的通用集合的合成及其在细胞色素P450蛋白的体外和细胞内三苯甲基-铁距离测量中的应用。