1-oxyl-4-(methylsulfonylamino)-2,2,6,6-tetramethylpiperidine | 69432-71-9

• 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: 1-oxyl-4-(methylsulfonylamino)-2,2,6,6-tetramethylpiperidine
• CAS: 69432-71-9
• 化学式: C₁₀H₂₁N₂O₃S
• 分子量: 249.354
• InChiKey: APSIYPXTNSNMLB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  58.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-oxyl-4-(methylsulfonylamino)-2,2,6,6-tetramethylpiperidine 在 盐酸 作用下， 以 乙醇 、 水 为溶剂， 反应 16.0h， 以94%的产率得到1-hydroxy-4-mesylamino-2,2,6,6-tetramethylpiperidinium chloride
  参考文献：
  名称：

  氧化还原三联体氧铵阳离子–硝氧基–羟胺中可逆歧化-歧化的动力学和热力学

  摘要：

  这些化合物的氧化还原和酸碱性质定义了环硝氧基自由基R 2 NO •与氧铵阳离子R 2 NO +和羟胺R 2 NOH的酸催化歧化反应的动力学和平衡。在最近的工作中（J. Phys。Org。Chem。2014，27，114-120），我们表明R 2 NO •在酸性介质中的动力学稳定性取决于硝酰基的碱性。在这里，我们研究了R 2 NO +和R 2 NOH与R 2 NO •的反比例歧化反应的动力学。并且发现取代基的-I效应的增加大大降低了反应K 4的总体平衡常数。这是由于羟基铵阳离子K 3H +的酸度常数的增加和氧铵阳离子E R2NO + / R2NO•与硝酰基自由基E R2NO•/ R2NOH的还原电位之间的差异所致。测定了水中羟胺E 1 /3Σ还原电位的pH依赖性以及羟胺R 2 NOH的键解离能D（OH）。对于各种各样的哌啶和吡咯烷-1-氧基值，p K3H +和ë R2NO + / R2NO•归属关系彼此，以及与平衡常数ķ

  DOI：

  10.1002/poc.3392
• 作为产物：
  描述：

  在 sodium tungstate (VI) dihydrate 、 双氧水 、 碳酸氢钠 作用下， 以 甲醇 、 水 为溶剂， 反应 4.0h， 以85%的产率得到1-oxyl-4-(methylsulfonylamino)-2,2,6,6-tetramethylpiperidine
  参考文献：
  名称：

  Preparation and Spectroscopic, Magnetic, and Electrochemical Studies of Mono-/Biradical TEMPO Derivatives

  摘要：

  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.

  DOI：

  10.1021/jo400845m

文献信息

• Heterobivalent Library Expansion by “Living Radical” Processes:  Thiocarbonyl Addition/Elimination, and Nitroxide-Based Reactions with Fluorous Deconvolution
  作者：David Crich、Daniel Grant、Albert A. Bowers

  DOI：10.1021/ja0756321

  日期：2007.10.1

  Degenerate radical addition fragmentation and nitroxide fragmentation reactions are applied to the expansion of heterobivalent libraries without contamination from homobivalent species. Deconvolution by means of a fluorous tagging process is described.
• Studies of Structure−Activity Relationship of Nitroxide Free Radicals and Their Precursors as Modifiers Against Oxidative Damage
  作者：Murali C. Krishna、William DeGraff、Olga H. Hankovszky、Cecília P. Sár、Tamás Kálai、József Jekő、Angelo Russo、James B. Mitchell、Kálmán Hideg

  DOI：10.1021/jm9802160

  日期：1998.8.1

  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.