tris(8-tert-butoxycarboxyl-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methyl | 1008756-99-7

• 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-tert-butoxycarboxyl-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methyl
• 英文别名: tris[8-tert-butoxycarbonyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']bis([1,3]dithiole)-4-yl]methyl radical；tris(8-tert-butoxycarbonyl-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methyl；tris[8-tert-butoxycarbonyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']bis([1,3]dithiol)-4-yl]methyl radical
• CAS: 1008756-99-7
• 化学式: C₅₂H₆₃O₆S₁₂
• 分子量: 1168.86
• InChiKey: SDIZHMDFNZKWSH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.9
• 重原子数：
  70
• 可旋转键数：
  12
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  383
• 氢给体数：
  0
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  tris(8-tert-butoxycarboxyl-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methyl 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 以40 %的产率得到
  参考文献：
  名称：

  具有可变反应性的羟甲基取代的四硫三芳基甲醇：通过独特的酸介导反应选择性获得三种不同的三苯甲基自由基

  摘要：

  描述了羟甲基取代的四硫代三芳基甲醇与不同酸的反应。反应条件针对三苯甲基自由基的羟甲基、甲基和醛衍生物及其氘代类似物的选择性合成进行了优化，这些衍生物表现出独特的 EPR 光谱和氧化还原特性，从而表明其适用于细胞内 EPR/动态核极化 (DNP) 。

  DOI：

  10.1002/ejoc.202400183
• 作为产物：
  描述：

  tris-(8-tert-butoxycarbonyl-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methanol 在 三氟化硼乙醚 、 tin(ll) chloride 作用下， 以 二氯甲烷 、 四氢呋喃 为溶剂， 以93.4%的产率得到tris(8-tert-butoxycarboxyl-2,2,6,6-tetramethylbenzo[1,2-d;4,5-d']bis[1,3]dithiol-4-yl)methyl
  参考文献：
  名称：

  作为细胞内氧探针的酯衍生四硫三芳基甲基自由基的合成和表征

  摘要：

  使用顺磁探针的电子顺磁共振 (EPR) 光谱已被用作准确测定生物系统中氧 (O 2 ) 浓度的重要工具。然而，顺磁探针仍然受到其细胞内穿透性的限制。合成并表征了各种酯化的三苯甲基衍生物，并确定了其中一个三苯甲基自由基的 X 射线结构。酯衍生的三苯甲基对 O 2表现出更高的敏感性浓度与三苯甲基三羧酸酯 CT-03 相比。还进行了循环伏安法以评估三苯甲基自由基对氧化和还原的敏感性。在研究的所有酯衍生的三苯甲基中，使用猪肝酯酶观察到乙酰氧基甲氧基酯容易水解为相应的羧酸酯。该研究表明，三苯甲基自由基的细胞渗透性可以通过改变酯基的类型和数量来实现。因此，酯衍生的三苯甲基自由基显示出作为细胞内 EPR 血氧饱和度探针和显像剂的巨大潜力。

  DOI：

  10.1021/jo7022747

文献信息

• Synthesis and Characterization of Ester-Derivatized Tetrathiatriarylmethyl Radicals as Intracellular Oxygen Probes
  作者：Yangping Liu、Frederick A. Villamena、Jian Sun、Yingkai Xu、Ilirian Dhimitruka、Jay L. Zweier

  DOI：10.1021/jo7022747

  日期：2008.2.1

  derivatives were synthesized and characterized, and an X-ray structure of one of the triyl radicals was determined. The ester-derivatized trityls exhibited higher sensitivity to O2 concentration compared to the trityl tricarboxylate CT-03. Cyclic voltammetry was also carried out to assess the susceptibility of the trityl radicals to oxidation and reduction. Among all of the ester-derivatized trityls studied,

  使用顺磁探针的电子顺磁共振 (EPR) 光谱已被用作准确测定生物系统中氧 (O 2 ) 浓度的重要工具。然而，顺磁探针仍然受到其细胞内穿透性的限制。合成并表征了各种酯化的三苯甲基衍生物，并确定了其中一个三苯甲基自由基的 X 射线结构。酯衍生的三苯甲基对 O 2表现出更高的敏感性浓度与三苯甲基三羧酸酯 CT-03 相比。还进行了循环伏安法以评估三苯甲基自由基对氧化和还原的敏感性。在研究的所有酯衍生的三苯甲基中，使用猪肝酯酶观察到乙酰氧基甲氧基酯容易水解为相应的羧酸酯。该研究表明，三苯甲基自由基的细胞渗透性可以通过改变酯基的类型和数量来实现。因此，酯衍生的三苯甲基自由基显示出作为细胞内 EPR 血氧饱和度探针和显像剂的巨大潜力。
• Triarylmethyl Radicals: An EPR Study of ¹³C Hyperfine Coupling Constants
  作者：Andrey A. Kuzhelev、Victor M. Tormyshev、Olga Yu. Rogozhnikova、Dmitry V. Trukhin、Tatiana I. Troitskaya、Rodion K. Strizhakov、Olesya A. Krumkacheva、Matvey V. Fedin、Elena G. Bagryanskaya

  DOI：10.1515/zpch-2016-0811

  日期：2017.4.1

  EPR methods for distance measurements in biomolecules. In this paper a large series of TAM radicals and their deuterated analogues is synthesized, and corresponding spectroscopic parameters including 13C hyperfine constants are obtained for the first time. The negligible dependence of 13C hyperfine constants on solvent, as well as on structure and number of substituents at para-C atoms of aromatic

  三芳基甲基 (TAM) 自由基广泛应用于电子顺磁共振 (EPR) 光谱中作为自旋标记，以及在 EPR 成像中作为体内血氧测定的自旋探针。TAM 的主要优势之一是 EPR 线极窄，特别是在氘代类似物 (~5 μT) 的情况下。另一个优点是即使在生理温度下它们的自旋弛豫速度也很慢，特别是允许应用脉冲偶极 EPR 方法进行生物分子的距离测量。本文合成了一系列TAM自由基及其氘代类似物，并首次获得了包括13C超精细常数在内的相应光谱参数。已发现 13C 超精细常数对溶剂以及芳环对位 C 原子取代基的结构和数量的依赖性可以忽略不计。此外，我们还证明，自然丰度的 13C 信号可用于使用脉冲电子双共振（PELDOR 或 DEER）成功进行室温距离测量。
• Synthesis, Characterization, and Nanoencapsulation of Tetrathiatriarylmethyl and Tetrachlorotriarylmethyl (Trityl) Radical Derivatives—A Study To Advance Their Applicability as in Vivo EPR Oxygen Sensors
  作者：Juliane Frank、Marwa Elewa、Mohamed M. Said、Hosam A. El Shihawy、Mohamed El-Sadek、Diana Müller、Annette Meister、Gerd Hause、Simon Drescher、Hendrik Metz、Peter Imming、Karsten Mäder

  DOI：10.1021/acs.joc.5b00918

  日期：2015.7.2

  Tissue oxygenation plays an important role in the pathophysiology of various diseases and is often a marker of prognosis and therapeutic response. EPR (ESR) is a suitable noninvasive oximetry technique. However, to reliably deploy soluble EPR probes as oxygen sensors in complex biological systems, there is still a need to investigate and improve their specificity, sensitivity, and stability. We reproducibly synthesized various derivatives of tetrathiatriarylmethyl and tetrachlorotriarylmethyl (trityl) radicals. Hydrophilic radicals were investigated in aqueous solution mimicking physiological conditions by, e.g., variation of viscosity and ionic strength. Their specificity was satisfactory, but the oxygen sensitivity was low. To enhance the capability of trityl radicals as oxygen sensors, encapsulation into oily core nanocapsules was performed. Thus, different lipophilic triesters were prepared and characterized in oily solution employing oils typically used in drug formulations, i.e., middle-chain triglycerides and isopropyl myristate. Our screening identified the deuterated ethyl ester of D-TAM (radical 13) to be suitable. It had an extremely narrow single EPR line under anoxic conditions and excellent oxygen sensitivity. After encapsulation, it retained its oxygen responsiveness and was protected against reduction by ascorbic acid. These biocompatible and highly sensitive nanosensors offer great potential for future EPR oximetry applications in preclinical research.
• Hydroxymethyl‐Substituted Tetrathiatriarylmethanol with Variable Reactivity: Selective Access to Three Different Trityl Radicals by Unique Acid‐Mediated Reactions
  作者：Yande Gao、Meirong Feng、Longfei Gao、Yurui Leng、Guifang Han、Yuguang Song、Yangping Liu

  DOI：10.1002/ejoc.202400183

  日期：——

  Reactions of hydroxymethyl-substituted tetrathiatriarylmethanol with different acids are described. The reaction conditions were optimized for the selective synthesis of hydroxymethyl, methyl and aldehyde derivatives of trityl radicals as well as their deuterated analogues, which exhibit distinct EPR spectra and redox properties, thus suggesting applicability to in-cell EPR/dynamic nuclear polarization

  描述了羟甲基取代的四硫代三芳基甲醇与不同酸的反应。反应条件针对三苯甲基自由基的羟甲基、甲基和醛衍生物及其氘代类似物的选择性合成进行了优化，这些衍生物表现出独特的 EPR 光谱和氧化还原特性，从而表明其适用于细胞内 EPR/动态核极化 (DNP) 。