3-bromo-4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl | 81635-38-3

• 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: 3-bromo-4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl
• 英文别名: 3-bromo-2,2,6,6-tetramethyl-1-oxyl-piperidine-4-one
• CAS: 81635-38-3
• 化学式: C₉H₁₅BrNO₂
• 分子量: 249.128
• InChiKey: ZPFWLGPYONUONX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  21.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-bromo-4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl 在 氢氧化钾 作用下， 反应 2.0h， 以77%的产率得到3-羧基-PROXYL
  参考文献：
  名称：

  A Study of the Favorskii Rearrangement with 3-Bromo-4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl

  摘要：

  Favorskii rearrangement reactions of the title compound with sodium hydroxide, sodium ethoxide, ammonia, several aliphatic amines, and ethyl sodiomalonate resulting in pyrrolidine nitroxyl radicals are described.

  DOI：

  10.1021/jo00116a029
• 作为产物：
  描述：

  4-氧-2,2,6,6-四甲基哌啶-1-氧自由基 在 盐酸 、 溴 作用下， 以 乙醇 、 氯仿 为溶剂， 反应 1.0h， 生成 3-bromo-4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl
  参考文献：
  名称：

  钴介导的自由基聚合和ATRP的结合合成聚乙酸乙烯酯和含聚乙烯醇的嵌段共聚物

  摘要：

  聚（乙酸乙烯酯）的低多分散性的酯（PVAc）链（中号瓦特/中号Ñ〜1.1-1.2）已经被制备乙酸乙烯酯的钴-介导的自由基聚合（VAC）。通过加入含氮氧化物的α-溴酸酯或α-溴代酮，它们已被活化的溴化物封端，并转化为有效的大分子引发剂，用于苯乙烯（Sty），丙烯酸乙酯和甲基丙烯酸甲酯的原子转移自由基聚合。由于每个嵌段都是通过受控过程形成的，因此易于制备定义明确的含PVAc的二嵌段共聚物。由α-溴酮封端的PVAc合成的PVAc- b -PS共聚物可以转化为定义明确的聚乙烯醇-b-聚苯乙烯两亲物通过聚乙酸乙烯酯嵌段的甲醇分解而得到。如通过透射电子显微镜观察到的，两亲性聚（乙烯醇）（3500）-b-聚苯乙烯（16600）在（4/1）水/四氢呋喃混合物中的自缔合导致形成囊泡。

  DOI：

  10.1021/ma051246x

文献信息

• Syntheses and Reactions of Pyrroline, Piperidine Nitroxide Phosphonates
  作者：Mostafa Isbera、Balázs Bognár、József Jekő、Cecilia Sár、Kálmán Hideg、Tamás Kálai

  DOI：10.3390/molecules25102430

  日期：——

  Horner-Wadsworth-Emmons (HWE) reactions. The reaction of paramagnetic α-bromoketone produced a vinylphosphonate in the Perkow reaction. Paramagnetic α-hydroxyphosphonates could be subjected to oxidation, elimination and substitution reactions to produce various paramagnetic phosphonates. The synthesized paramagnetic phosphonates proved to be useful synthetic building blocks for carbon-carbon bond-forming reactions

  有机磷化合物在众多有机化合物中占据重要地位，但已报道的顺磁性磷化合物数量有限，包括顺磁性膦酸盐。本文描述了吡咯啉和哌啶硝基氧膦酸酯的合成和进一步转化，这些方法采用成熟的方法，例如 Pudovik、Arbuzov 和 Horner-Wadsworth-Emmons (HWE) 反应。顺磁性 α-溴酮的反应在 Perkow 反应中产生了乙烯基膦酸酯。顺磁性 α-羟基膦酸酯可以进行氧化、消除和取代反应以产生各种顺磁性膦酸酯。合成的顺磁性膦酸酯被证明是霍纳-沃兹沃思-埃蒙斯烯化反应中碳-碳键形成反应的有用合成构件。获得的不饱和化合物可以转化为各种取代的吡咯啉氮氧化物、proxyl氮氧化物和顺磁性多环芳烃。还筛选了新膦酸盐的 Trolox® 等效抗氧化能力 (TEAC)，叔 α-羟基膦酸盐硝基氧表现出显着的抗氧化活性。
• Synthesis of Novel Bicyclic Nitroxides Using Partial Favorskii Rearrangement
  作者：Andrej Babič、Slavko Pečar

  DOI：10.1055/s-2008-1072715

  日期：2008.5

  1-oxyl was reacted with several C-nucleophiles to give novel bicyclic pyrrolidine nitroxides through partial Favorskii rearrangement. Further reduction with sodium borohydride gave spin probes with free hydroxyl groups and under harsh reduction conditions allowed the Favorskii rearrangement to proceed to completion.

  3-Bromo-2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl 与几种 C-亲核试剂反应，通过部分 Favorskii 重排得到新型双环吡咯烷氮氧化物。用硼氢化钠进一步还原得到带有游离羟基的自旋探针，并且在苛刻的还原条件下允许 Favorskii 重排进行到完成。
• A Short Way to Esters of 1-Oxyl-2,2,5,5-Tetramethylpyrrolidine-3-carboxylic Acid by Favorski Rearrangement
  作者：Gašper Marc、Slavko Pečar

  DOI：10.1080/00397919508012662

  日期：1995.4

  Abstract The reaction of 3-bromo-4-oxo-l-oxyl-2,2,6,6-tetramethylpiperidine (1) with a solid sodium, alkoxide of primary or secondary alcohol provides a short way to prepare ester of 3-carboxy-1-oxyl-2,2,5,5-tetramethylpyrrolidine where the ring contraction from six (1) to five (6a-f) in a Favorski rearrangement occurs.

  摘要 3-bromo-4-oxo-l-oxyl-2,2,6,6-四甲基哌啶 (1) 与固体伯醇或仲醇钠、醇盐的反应为制备 3-羧基酯提供了一条捷径。 -1-oxyl-2,2,5,5-四甲基吡咯烷，在 Favorski 重排中环从六 (1) 收缩到五 (6a-f)。
• 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.
• Dikanov, S. A.; Grigor'ev, I. A.; Volodarskii, L. B., Russian Journal of Physical Chemistry, 1982, vol. 56, # 11, p. 1696 - 1699
  作者：Dikanov, S. A.、Grigor'ev, I. A.、Volodarskii, L. B.、Tsvetkov, Yu. D.

  DOI：——

  日期：——