tris[2,2,6,6-(²H₃-tetramethyl)benzo[1,2-d:4,5-d']bis([1,3]dithiole)-4-yl]methanol | 179555-79-4

• 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[2,2,6,6-(²H₃-tetramethyl)benzo[1,2-d:4,5-d']bis([1,3]dithiole)-4-yl]methanol
• 英文别名: tris(2,2,6,6-tetramethyl-(d12)-benzo[1,2-d;4,5-dc]bis[1,3]dithiol-4-yl)methanol
• CAS: 179555-79-4
• 化学式: C₃₇H₄₀OS₁₂
• 分子量: 921.23
• InChiKey: ZOUXGFTUOFEGHE-MCDHJEQXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.57
• 重原子数：
  50.0
• 可旋转键数：
  15.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  13.0

反应信息

• 作为反应物：
  描述：

  二碳酸二叔丁酯 、 tris[2,2,6,6-(²H₃-tetramethyl)benzo[1,2-d:4,5-d']bis([1,3]dithiole)-4-yl]methanol 在 正丁基锂 、 四甲基乙二胺 作用下， 以 正己烷 、 苯 为溶剂， 以50%的产率得到tris[8-tert-butoxycarbonyl-2,2,6,6-(2H3-tetramethyl)benzo[1,2-d:4,5-d']bis([1,3]dithiole)-4-yl]methanol
  参考文献：
  名称：

  芬兰三苯甲基氘代衍生物的合成、结构和 EPR 表征

  摘要：

  取代的三苯甲基自由基是重要的自旋探针，用于功能性电子顺磁共振波谱和成像，包括体内氧气和 pH 值绘图。在这里，我们报告了大规模合成氘代芬兰三苯甲基自由基的合成程序，该过程具有优异的 EPR 光谱特性和对溶液中氧浓度的更高灵敏度。此外，芬兰三苯甲基自由基被适合连接肽或其他合成前体的接头取代。已经评估了氘代取代对同源衍生物的 EPR 光谱的影响。这些化合物是 EPR 成像中靶向自旋探针的潜在候选者。

  DOI：

  10.1016/j.bmcl.2010.05.006
• 作为产物：
  描述：

  2,2,6,6-tetra(²H₃-methyl)benzo[1,2-d:4,5-d']bis[1,3]dithiole 、 氯甲酸甲酯 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 2.0h， 以43.4%的产率得到tris[2,2,6,6-(²H₃-tetramethyl)benzo[1,2-d:4,5-d']bis([1,3]dithiole)-4-yl]methanol
  参考文献：
  名称：

  芬兰三苯甲基氘代衍生物的合成、结构和 EPR 表征

  摘要：

  取代的三苯甲基自由基是重要的自旋探针，用于功能性电子顺磁共振波谱和成像，包括体内氧气和 pH 值绘图。在这里，我们报告了大规模合成氘代芬兰三苯甲基自由基的合成程序，该过程具有优异的 EPR 光谱特性和对溶液中氧浓度的更高灵敏度。此外，芬兰三苯甲基自由基被适合连接肽或其他合成前体的接头取代。已经评估了氘代取代对同源衍生物的 EPR 光谱的影响。这些化合物是 EPR 成像中靶向自旋探针的潜在候选者。

  DOI：

  10.1016/j.bmcl.2010.05.006

文献信息

• 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.
• Phosphonated Trityl Probes for Concurrent in Vivo Tissue Oxygen and pH Monitoring Using Electron Paramagnetic Resonance-Based Techniques
  作者：Ilirian Dhimitruka、Andrey A. Bobko、Timothy D. Eubank、Denis A. Komarov、Valery V. Khramtsov

  DOI：10.1021/ja401572r

  日期：2013.4.17

  Previously we proposed the concept of dual function pH and oxygen paramagnetic probes based on the incorporation of ionizable groups into the structure of persistent triarylmethyl radicals, TAMs (J. Am. Chem. Soc. 2007, 129, 7240-7241). In this paper, we synthesized an asymmetric monophosphonated TAM probe with the simplest doublet hfs pattern ideally suited for dual function electron paramagnetic resonance (EPR)-based applications. An extraordinary low line width of the synthesized deuterated derivative, p(1)TAM-D (Delta H-pp <= 50 mG, Lorentz line width, <= 20 mG) results in high sensitivity to pO(2) due to oxygen-induced line broadening (Delta LW/Delta pO(2) approximate to 0.5 mG/mmHg or approximate to 400 mG/mM); accuracy of pO(2) measurement, approximate to 1 mmHg). The presence of a phosphono group in the p(1)TAM-D structure provides pH sensitivity to its EPR spectra in the physiological range of pH from 5.9 to 8.2 with the ratio of signal intensities of protonated and deprotonated states being a reliable pH marker (accuracy of pH measurements, +/- 0.05). The independent character of pH and [O-2] effects on the EPR spectra of p(1)TAM-D provides dual functionality to this probe. The L-band EPR studies performed in breast tumor-bearing mice show a significant difference in extracellular pH and pO(2) between tumor and normal mammary gland tissues, as well as the effect of animal breathing with 100% O-2 on tissue oxygenation. The developed dual function phosphonated p(1)TAM-D probe provides a unique tool for in vivo concurrent tissue oxygen and pH monitoring.