bis-(4-amino-2,2,6,6-tetramethyl piperidinooxyl) | 64509-42-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: bis-(4-amino-2,2,6,6-tetramethyl piperidinooxyl)
• 英文别名: N,N-bis(1-yloxy-2,2,6,6-tetramethylpiperidin-3-yl)amine；N,N-bis(1-oxido-2,2,6,6-tetramethylpiperidin-4-yl)amine；N,N-bis(2,2,6,6-tetramethylpiperidinyl-1-oxy)amine；4-amino-2,2,6,6-tetramethyl-N-(2,2,6,6-tetramethyl-1-oxylpiperidin-4-yl)piperidine-1-oxyl；N,N-di(TEMPO)amine；2,2,6,6-tetramethyl-1-oxido-N-(2,2,6,6-tetramethyl-1-oxopiperidin-1-ium-4-yl)piperidin-4-amine
• CAS: 64509-42-8
• 化学式: C₁₈H₃₅N₃O₂
• 分子量: 325.495
• InChiKey: GYOQMHXXZXONKH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis-(4-amino-2,2,6,6-tetramethyl piperidinooxyl) 在 盐酸 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以61%的产率得到1-hydroxy-N-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)-2,2,6,6-tetramethylpiperidin-4-amine;hydrochloride
  参考文献：
  名称：

  Studies of Structure−Activity Relationship of Nitroxide Free Radicals and Their Precursors as Modifiers Against Oxidative Damage

  摘要：

  The protective effects of stable nitroxides, as well as their hydroxylamine and amine precursors, have been tested in Chinese hamster V79 cells subjected to H2O2 exposure at fixed concentration or exposure to ionizing radiation. Cytotoxicity was evaluated by monitoring the viability of the cells assessed by the clonogenic assay. The compounds tested at fixed concentration varied in terms of ring size, oxidation state, and ring substituents. Electrochemical studies were carried out to measure the redox midpoint potentials. The studies show that in the case of protection against H2O2 exposure, the protection was determined by the ring size, oxidation state, and redox midpoint potentials. In general the protection factors followed the order nitroxides > hydroxylamines > amines. Both the six-membered ring nitroxides and substituted five-membered ring nitroxides were efficient protectors. For six-membered ring nitroxides, the compounds exhibiting the lowest midpoint potentials exhibited maximal protection. In the case of X-radiation, nitroxides were the most protective though some hydroxylamines were also efficient. The amines were in some cases found to sensitize the toxicity of aerobic radiation exposure. The protection observed by the nitroxides was not dependent on the ring size. However, the ring substituents had significant influence on the protection. Compounds containing a basic side chain were found to provide enhanced protection. The results in this study suggest that these compounds are novel antioxidants which can provide cytoprotection in mammalian cells against diverse types of oxidative insult and identify structural determinants optimal for protection against individual types of damage.

  DOI：

  10.1021/jm9802160
• 作为产物：
  描述：

  4-氧-2,2,6,6-四甲基哌啶-1-氧自由基 在 三氟乙酸铵 作用下， 以75%的产率得到bis-(4-amino-2,2,6,6-tetramethyl piperidinooxyl)
  参考文献：
  名称：

  三乙酰氧基硼氢化钠在合成氮氧化物双自由基中的用途

  摘要：

  合成了一系列氮氧化物双自由基，其目的是产生具有高度弛豫性的末端基团，以连接至树枝状聚合物，以用作关节软骨的靶向MR造影剂。一氧化氮双自由基的结构强烈影响其MR弛豫性。在硝酰基环和桥键之间添加一个碳原子氮通过使单体氮氧化物的弛豫度增加一倍，使氮自由基双自由基的弛豫度提高了约14％。相反，在不含额外碳原子的氮氧化物双自由基中，空间位阻将弛豫度限制在比将单体氮氧化物的弛豫度加倍的预期值低约35％的位置。在硝基氧基环和桥键之间结合了碳原子的一氧化二氮自由基氮MR弛豫度比相应的单体一氧化氮大约223％。通过将这些氮氧化物双自由基与树枝状聚合物连接，应该可以合成具有比以单个腈氧基环为末端基团的树枝状聚合物连接的氮氧化物更高的弛豫度的靶向磁共振造影剂。这些与树状聚合物连接的二硝基氧化物应能够根据正常情况区分正常和异常的软骨。糖胺聚糖 专注。

  DOI：

  10.1039/b208263b

文献信息

• Water-proton relaxivity of hyperbranched polymers carrying TEMPO radicals
  作者：Hiroyuki Hayashi、Satoru Karasawa、Akihiro Tanaka、Keisuke Odoi、Katsumi Chikama、Hideto Kuribayashi、Noboru Koga

  DOI：10.1002/mrc.2384

  日期：2009.3

  polymers carrying stable 2, 2, 6, 6‐tetramethylpiperidine‐1‐oxyl (TEMPO) radicals, HPS‐N‐TEMPO, HPS‐Im‐TEMPO, and HPS‐Im‐(TEMPO)2, were prepared in ca. 60% introducing yield. HPS‐N‐TEMPO and HPS‐Im‐TEMPO were determined to be nearly spherical shapes of the diameter of 2.4 ± 0.6 and 2.2 ± 0.6 nm, respectively, by transmission electron microscope (TEM) images. The values of water‐proton relaxivity, r1, at

  高水溶性超支化聚 (苯乙烯) (HPS) 聚合物携带稳定的 2, 2, 6, 6-四甲基哌啶-1-氧基 (TEMPO) 自由基、HPS-N-TEMPO、HPS-Im-TEMPO 和 HPS-Im- (TEMPO)2，在大约。60% 引入收率。通过透射电子显微镜 (TEM) 图像确定 HPS-N-TEMPO 和 HPS-Im-TEMPO 分别为直径为 2.4 ± 0.6 和 2.2 ± 0.6 nm 的近球形。HPS-N-TEMPO、HPS-Im-TEMPO 和 HPS-在 25 MHz、0.59 T 和 25 °C 下的水质子弛豫率 r1 值为 6.0、5.2 和 14 mM-1 sec-1分别为 Im-(TEMPO)2。还观察到体模中的自旋晶格弛豫时间 (T1) 加权图像。版权所有 © 2009 John Wiley & Sons, Ltd.
• Polyradical PROXYL/TEMPO-Derived Amides: Synthesis, Physicochemical Studies, DFT Calculations, and Antimicrobial Activity
  作者：Patrik Poprac、Peter Poliak、Miroslav Kavala、Zuzana Barbieriková、Michal Zalibera、Marek Fronc、Ľubomír Švorc、Zuzana Vihonská、Petra Olejníková、Karol Lušpai、Vladimír Lukeš、Vlasta Brezová、Peter Szolcsányi

  DOI：10.1002/cplu.201700343

  日期：2017.11

  A series of polynitroxide amides possessing 2,2,5,5-tetramethyl-1-pyrrolidinyloxy (PROXYL) and/or 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) units connected through various bridges were synthesized and their properties were analyzed. EPR spectroscopy provided detailed insight into their paramagnetic character and related properties. A thorough examination of the EPR spectra of dinitroxides in organic

  合成了一系列具有2,2,5,5-四甲基-1-吡咯烷基氧基（PROXYL）和/或2,2,6,6-四甲基-1-哌啶基氧基（TEMPO）单元的聚硝基氧酰胺，并通过各种桥连接性能进行了分析。EPR光谱学提供了对其顺磁性特征和相关特性的详细了解。彻底检查有机溶剂中二硝基氧化物的EPR光谱可提供有关分子内运动，热力学和自旋交换机制的有价值的信息。对溶解的二硝基氧化物的低温X波段和Q波段EPR谱的分析提供了自旋-自旋距离，该距离可与DFT获得的理论值相媲美。循环伏安法研究揭示了PROXYL衍生的双基自由基的（准）可逆电化学行为，而发现含有TEMPO的双自由基和多自由基的可逆性显着降低。评估了氮氧化物对模型细菌，酵母和丝状真菌的抑制活性。
• Synthesis, physicochemical properties and antimicrobial activity of mono-/dinitroxyl amides
  作者：Miroslav Kavala、Vlasta Brezová、Ľubomír Švorc、Zuzana Vihonská、Petra Olejníková、Ján Moncol、Jozef Kožíšek、Peter Herich、Peter Szolcsányi

  DOI：10.1039/c4ob00302k

  日期：——

  Two comparative sets of mono-/dinitroxyl amides were designed and prepared. The novel TEMPO and/or PROXYL derivatives were fully characterised and their spin, redox and antimicrobial properties were determined. Cyclic voltammetry revealed (quasi)reversible redox behavior for most of the studied radicals. Moreover, the electron-withdrawing substituents increased the oxidation potential of nitroxides

  设计并制备了两套比较的单/二硝基甲酰胺。对新型TEMPO和/或PROXYL衍生物进行了全面表征，并确定了它们的自旋，氧化还原和抗菌性能。循环伏安法揭示了大多数已研究自由基的（准）可逆氧化还原行为。而且，与给电子基团相比，吸电子取代基增加了氮氧化物的氧化电势。单自由基的EPR光谱具有典型的三线信号，而双自由基的光谱则显示出更复杂的分裂模式。在体外生物测定揭示了不同于吡咯衍生物，哌啶氮氧自由基显著抑制的生长葡萄球菌属。
• The first example of the use of 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl in the Mannich reaction to obtain radical-labeled bispidines
  作者：A. V. Medved’ko、M. O. Ermakov、S. Z. Vatsadze

  DOI：10.1007/s11172-024-4266-y

  日期：2024.5

  Bispidine containing a paramagnetic group was obtained for the first time by the Mannich reaction using the 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-amino-TEMPO) free radical as a reagent. The structure of the target compound, tert-butyl 9-oxo-7-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-3,7-diazabicyclo[3.3.1]nonane-3-carboxylate, was confirmed by mass spectrometry and ESR spectroscopy, the

  以4-氨基-2,2,6,6-四甲基哌啶-1-氧基(4-氨基-TEMPO)自由基为试剂，通过曼尼希反应首次获得了含有顺磁性基团的双吡啶。目标化合物叔丁基9-氧代-7-(1-氧基-2,2,6,6-四甲基哌啶-4-基)-3,7-二氮杂双环[3.3.1]壬烷-3-的结构通过质谱和ESR光谱证实了其为羧酸盐，并通过X射线衍射分析建立了分子和晶体结构。在通过还原胺化反应合成起始4-氨基-TEMPO时，4-氨基-TEMPO与起始酮进一步反应的副产物，游离双自由基N-(2,2,6,6-分离并表征了四甲基-1-氧基哌啶-4-基)-2,2,6,6-四甲基-4-氨基哌啶-1-氧基。
• Preparation and Spectroscopic, Magnetic, and Electrochemical Studies of Mono-/Biradical TEMPO Derivatives
  作者：Miroslav Kavala、Roman Boča、Lubomír Dlháň、Vlasta Brezová、Martin Breza、Jozef Kožíšek、Marek Fronc、Peter Herich、Lubomír Švorc、Peter Szolcsányi

  DOI：10.1021/jo400845m

  日期：2013.7.5

  A comparison set of mono-/biradical TEMPO derivatives was prepared, novel compounds were fully characterized, and their physicochemical properties were determined. Cyclic voltammetry revealed reversible redox behavior for all studied nitroxides. Moreover, the electron-withdrawing substituents increased the oxidation potential of the respective nitroxides in comparison to electron-donating groups. While EPR spectra of monoradicals in dichloromethane at 295 K reveal the expected three-line signal, spectra of biradicals show more complex features. DFT and MP2 calculations indicate that the EPR splitting pattern of dinitroxide 7 could be explained by its interactions with solvent molecules. In the solid state, mononitroxides 4 and 5 behave as a Heisenberg antiferromagnetic chain, whereas dinitroxides 6-8 are almost isolated paramagnetic diradicals coupled in an antiferromagnetic manner.