4-(N,N-dimethylamino)-2,2,6,6-tetramethylpiperidin-1-oxyl | 71335-68-7

• 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: 4-(N,N-dimethylamino)-2,2,6,6-tetramethylpiperidin-1-oxyl
• 英文别名: N,N,2,2,6,6-hexamethylpiperidinyloxy-4-amine；4-(dimethylamino)-2,2,6,6-tetramethylpiperidinyl-1-oxy；4-(N,N-dimethylamino)-TEMPO；DMAT；2,2,6,6-tetramethyl-4-dimethylamino-piperidinyloxy；4-dimethylamino-2,2,6,6-tetramethyl-piperidinyloxy；4-dimethylamino-TEMPO
• CAS: 71335-68-7
• 化学式: C₁₁H₂₃N₂O
• 分子量: 199.316
• InChiKey: RUAAVFPWYWKTIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  7.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(N,N-dimethylamino)-2,2,6,6-tetramethylpiperidin-1-oxyl 在 苯肼 作用下， 以 丙酮 为溶剂， 反应 36.0h， 生成
  参考文献：
  名称：

  [EN] IONIC CYCLIC NITROXYL RADICAL OLIGOMERS
  [FR] OLIGOMÈRES IONIQUES DE RADICAUX NITROXYLES CYCLIQUES

  摘要：

  Ionic cyclic nitroxyl radical oligomers, methods of making the ionic cyclic nitroxyl radical oligomers, and electrochemical cells, such as aqueous organic redox flow batteries (AORFBs) that use the ionic nitroxyl radical oligomers as catholytes are provided. The oligomers are larger than individual cyclic nitroxyl radical molecules, but maintain a high density nitroxyl radical groups within the molecule. As a result, when the oligomers are used as catholytes in an AORFB, they are able to reduce catholyte permeation through the ion-conducting membrane, while providing a high volumetric capacity and cycling stability.

  公开号：

  WO2022251610A1
• 作为产物：
  描述：

  4-二甲氨基-2,2,6,6-四甲基哌啶 在 magnesium hydroxide 、 双氧水 作用下， 以 水 为溶剂， 反应 14.0h， 以98%的产率得到4-(N,N-dimethylamino)-2,2,6,6-tetramethylpiperidin-1-oxyl
  参考文献：
  名称：

  一种TEMPO-4-氯化铵的制备方法

  摘要：

  本发明涉及领域，具体提供了一种TEMPO‑4‑氯化铵的制备方法，包括如下步骤：S1将三丙酮胺与二甲胺加入水中，然后加入加氢催化剂进行加氢还原反应，得到N,N,2,2,6,6‑六甲基哌啶基‑4‑胺；S2在催化剂作用下，N,N,2,2,6,6‑六甲基哌啶基‑4‑胺与双氧水在溶剂中进行氧化反应，得到N,N,2,2,6,6‑六甲基哌啶基氧基‑4‑胺；S3将N,N,2,2,6,6‑六甲基哌啶基氧基‑4‑胺加入非质子溶剂中，然后通入氯甲烷，反应得到目标产物TEMPO‑4‑氯化铵，本发明的原料转化率高，溶剂绿色环保，且可直接进入下一步进行氧化反应操作；反应整体工序简单易操作，提纯步骤少、产物纯度高，成本低廉，原子经济，符合绿色生产的理念。

  公开号：

  CN113666864A

文献信息

• Antiferromagnetic ordering based on intermolecular London dispersion interactions in amphiphilic TEMPO ammonium salts
  作者：Jessica Exner、Steffen Eusterwiemann、Oliver Janka、Carsten Doerenkamp、Anja Massolle、Oliver Niehaus、Constantin G. Daniliuc、Rainer Pöttgen、Johannes Neugebauer、Armido Studer、Hellmut Eckert

  DOI：10.1039/c8cp05837g

  日期：——

  Antiferromagnetic coupling in TEMPO-based radicals can be enhanced via self-assembly through London dispersion interactions in amphiphilic solids. The synthesis, magnetic characterization, and three crystal structures of the solid radical ion salts (R-DMAT-n)X with various counterions X and alkyl chain lengths n are reported. Magnetic susceptibility and absolute EPR signal intensity measurements show

  TEMPO基自由基中的反铁磁耦合可通过两亲固体中的伦敦分散相互作用通过自组装增强。报道了具有各种抗衡离子X和烷基链长n的固体自由基离子盐（R-DMAT- n）X的合成，磁性表征和三种晶体结构。磁化率和绝对EPR信号强度测量在许多情况下都显示出单重态-三重态跃迁，这与晶体结构有关。反铁磁有序效应对烷基链和抗衡阴离子的长度均敏感。
• CT complexes based on TEMPO radicals
  作者：Shin'ichi Nakatsuji、Atsushi Takai、Kazuyoshi Nishikawa、Yukio Morimoto、Noritake Yasuoka、Kazuya Suzuki、Toshiaki Enoki、Hiroyuki Anzai

  DOI：10.1039/a900295b

  日期：——

  A series of CT (charge-transfer) complexes have been prepared, in which TEMPO (2,2,6,6-tetramethylpiperidinyloxyl) radical 1 and its derivatives (2 and 6-10) act as donors using TCNQF 4 (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) or DDQ (2,3-dichloro-5,6-dicyanobenzo-1,4-quinone) as acceptors. A sharp difference was observed in magnetic properties between the charge-transfer complexes derived from the TEMPO radicals 1 or 2 and amino-TEMPO radicals 6-10 and the distinct difference observed in the molecular/crystal structures in the complexes is thought to reflect the difference in their magnetic behaviour. The CT complexes from 4-dimethylamino- or 4-azetidino-TEMPO and DDQ formed salt-like complexes of protonated 4-dialkylamino-TEMPO and the substituted benzo-1,4-quinonehydroxylate upon recrystallization from moist acetone.TEMPO radicals are a well-known class of stable radicals mainly used as spin probes for biological studies and a number of derivatives have been prepared for the purpose until now. 1 On the other hand, it is of current interest to develop new molecular-based magnetic materials especially organomagnetic materials and numerous compounds carrying TEMPO radicals as the key building blocks have been prepared and their magnetic behaviour has been elucidated in recent years. 2 During the course of our studies to develop new organomagnetic materials, we have been interested in preparing some donor or acceptor molecules carrying stable radicals and the CT complexes derived therefrom to build up and to arrange the spins in the solid state/crystal structures 4 and we found recently that some TEMPO radicals (A) 5 or verdazyl radicals (B) 6

  一系列CT（电荷转移）配合物已被制备，其中TEMPO（2,2,6,6-四甲基哌啶氧化氮）自由基1及其衍生物（2和6-10）作为供体，使用TCNQF 4（2,3,5,6-四氟-7,7,8,8-四氰基喹啉二甲烷）或DDQ（2,3-二氯-5,6-二氰基苯-1,4-醌）作为受体。从TEMPO自由基1或2和氨基-TEMPO自由基6-10衍生出的电荷转移配合物在磁性性质上观察到显著差异，而在配合物分子/晶体结构中观察到的差异被认为是反映了它们磁性行为的差异。从4-二甲基氨基-或4-氮杂环丁烷-TEMPO与DDQ形成的CT配合物，在湿润丙酮中重结晶后，形成了质子化的4-二烷基氨基-TEMPO和取代的苯-1,4-醌羟酸盐类配合物。TEMPO自由基是一类已知的稳定自由基，主要用作生物研究的自旋探针，迄今为止已制备了许多衍生物。 另一方面，发展基于分子的新型磁性材料尤其是有机磁性材料是当前的研究兴趣所在，近年来已经制备了大量含有TEMPO自由基作为关键构建单元的化合物，并阐明了它们的磁性行为。在我们开发新型有机磁性材料的研究过程中，我们一直对制备一些含有稳定自由基的供体或受体分子以及由此衍生的CT配合物感兴趣，以构建和排列固态/晶体结构中的自旋，我们最近发现了一些TEMPO自由基（A）或凡扎自由基（B）。
• Synthesis of unsymmetrical spin-labelled bolaamphiphiles
  作者：Mathieu Berchel、Loïc Lemiègre、Jelena Jeftić、Thierry Benvegnu

  DOI：10.1016/j.tetlet.2008.05.125

  日期：2008.8

  This work presents the efficient synthesis of a novel spin-labelled bolaamphiphile bearing sugar and cationic polar heads. Preliminary ESR studies were conduced both in CH2Cl2 and water and have confirmed that this methodology can be used to study the transversal rotation (flip–flop) dynamic of membrane involving such bolaamphiphiles.

  这项工作提出了一种新型的带有糖和阳离子极性头的自旋标记的双亲两亲物的有效合成。在CH 2 Cl 2和水中均进行了初步的ESR研究，并证实该方法可用于研究涉及此类双性两亲物的膜的横向旋转（触发器）动力学。
• Synthesis and characterization of amorphous mesoporous silica using TEMPO-functionalized amphiphilic templates
  作者：Wilke de Vries、Carsten Doerenkamp、Zhaoyang Zeng、Marcos de Oliveira、Oliver Niehaus、Rainer Pöttgen、Armido Studer、Hellmut Eckert

  DOI：10.1016/j.jssc.2016.01.023

  日期：2016.5

  Inorganic–organic hybrid materials based on amorphous mesoporous silica containing organized nitroxide radicals within its mesopores have been prepared using the micellar self-assembly of TEOS solutions containing the nitroxide functionalized amphiphile (4-(N,N-dimethyl-N-hexadecylammonium)-2,2,6,6-tetramethyl-piperidin-N-oxyl-iodide) (CAT-16). This template has been used both in its pure form and

  使用包含氮氧化物官能化两亲物（4-（N，N-二甲基-N-十六烷基铵）-2 （2,6,6-四甲基哌啶-N-氧基碘）（CAT-16）。该模板既可以以其纯净形式使用，也可以与十六烷基三甲基溴化铵（CTAB）混合使用。样品已通过化学分析表征，N 2吸附研究，磁化率测量和各种光谱方法。电子顺磁共振（EPR）光谱表明分子间自旋-自旋相互作用的强度可以通过CAT-16 / CTAB比率来控制，而核磁共振（NMR）数据表明这些相互作用太弱而无法促进协同磁性。
• Magnetic properties of charge-transfer complexes based on TEMPO radicals
  作者：Shin’ichi Nakatsuji、Atsushi Takai、Kazuyoshi Nishikawa、Yukio Morimoto、Noritake Yasuoka、Kazuya Suzuki、Toshiaki Enoki、Hiroyuki Anzai

  DOI：10.1039/a606293h

  日期：——

  TEMPO (2,2,6,6-tetramethylpiperidinyloxy) radical 1 and its derivatives 2–5 are found to form charge-transfer complexes with some acceptors such as TCNQF 4 (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) or DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) being isolated as solid substances.

  研究发现，TEMPO（2,2,6,6-四甲基哌啶基氧基）自由基 1 及其衍生物 2-5 能与一些受体（如 TCNQF 4（2,3,5,6-四氟-7,7,8,8-四氰基二甲烷）或 DDQ（2,3-二氯-5,6-二氰基-1,4-苯醌））形成电荷转移络合物，并分离出固体物质。