2-bromo-4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl | 21431-61-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: 2-bromo-4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl
• CAS: 21431-61-8
• 化学式: C₇H₁₂BrN₂O₂
• 分子量: 236.088
• InChiKey: WXHKTGXPFYVJRI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-bromo-4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl 在 sodium hydride 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 30.17h， 生成 2-(benzotriazol-1-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl
  参考文献：
  名称：

  Syntheses and structures of azol-1-yl derivatives of nitronyl and imino nitroxides

  摘要：

  2-(Pyrazol-1-yl)-, 2-(imidazol-1-yl)-, 2-([1,2,4]triazol-1-yl)-, and 2-(benzotriazol-1-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl were prepared by reactions of 2-bromo-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (NIT-Br) with the corresponding sodium azolides. In prepared 2-(azol-1-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyls, the NIT-N-Het bond is readily hydrolyzed. Reduction of imidazole-3-oxide-1-oxyls leads to corresponding 2-(azol-1-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyls, which are much more stable against hydrolysis. The structures of spin-labeled imidazoles, [1,2,4]triazoles and benzotriazoles are confirmed by X-ray analysis, showing that the paramagnetic molecules form packings with motifs from centrosymmetric dimers to topologically linear chains. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.10.087
• 作为产物：
  描述：

  4,4,5,5-tetramethylimidazolin-1-oxyl-3-oxide 在 sodium hypobromide 作用下， 反应 0.01h， 以84%的产率得到2-bromo-4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl
  参考文献：
  名称：

  源自胺基自旋极化供体的高自旋阳离子双自由基的设计、制备和电子结构

  摘要：

  合成了基于胺的供体自由基，如二甲氨基、二乙氨基和吗啉硝基氮氧化物，并通过循环伏安法检查了它们的供体能力。单氧化供体自由基的 ESR 光谱显示来自这些供体自由基的阳离子自由基的基态三线态信号。结果是通过产生的 π-自旋和自由基单元上的局部未配对电子之间存在铁磁耦合来解释的。根据分子轨道计算，这两个自旋之间的铁磁耦合源于位于自由基单元上的 SOMO 和由单电子氧化时供体自由基的 HOMO 衍生的 SOMO' 之间的空间共享性质。所以，这些供体自由基的阳离子自由基可以被认为是三亚甲基甲烷的杂类似物。为了扩展供体单元的π-电子结构，合成了对和间二甲氨基苯基硝酰基氮氧化合物，并...

  DOI：

  10.1021/ja994547t

文献信息

• Design and preparation of pyrrole-based spin-polarized donorsElectronic supplementary information (ESI) available: cyclic voltammograms for N-PN, β-PN, N-TPN, PhNN and TPP. See http://www.rsc.org/suppdata/jm/b2/b211986b/
  作者：Jotaro Nakazaki、InGwon Chung、Michio M. Matsushita、Tadashi Sugawara、Ryoji Watanabe、Akira Izuoka、Yuzo Kawada

  DOI：10.1039/b211986b

  日期：2003.4.16

  As a fundamental building block of a conductive magnetic macromolecule, a series of pyrrole derivatives carrying a nitronyl nitroxide (NN) group was prepared. Some of these derivatives afforded ground-state triplet diradical cations upon one-electron oxidation, and the difference in the spin multiplicities of the singly oxidized pyrrolylNNs was rationalized on the basis of a perturbational molecular orbital method. The electronic interaction between the pyrrole and the nitronyl nitroxide parts was also confirmed by cyclic voltammetry and UV-Vis absorption spectroscopy. In spite of the vacancy of the 2 and 5 positions of the pyrrole ring, electrochemical polymerization of these derivatives was not observed, except for an extended α-thienyl derivative.

  作为导电磁性大分子的基本构件，我们制备了一系列带有硝基亚硝氧（NN）基团的吡咯衍生物。其中一些衍生物在单电子氧化时产生基态三重二极阳离子，并根据扰动分子轨道方法合理解释了单氧化吡咯基 NN 的自旋倍率差异。循环伏安法和紫外可见吸收光谱也证实了吡咯和硝基亚硝基之间的电子相互作用。尽管吡咯环的 2 号和 5 号位置存在空位，但除了一种扩展的 α-thienyl 衍生物外，没有观察到这些衍生物的电化学聚合反应。
• STRUCTURE OF A Pd–ORGANIC PARAMAGNETIC
  作者：G. V. Romanenko、S. V. Fokin、A. S. Bogomyakov、V. I. Ovcharenko

  DOI：10.1134/s0022476620120136

  日期：2020.12

  By the interaction of 2-bromo-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (NN–Br) with tetrakis(triphenylphosphine)palladium(0) a new paramagnetic palladium-organic compound [Pd(NN)(PPh3)2Br] is synthesized. The crystal structure of its tetrahydrofuran solvate is determined by X-ray diffraction. The obtained data allow us to expect that the effective Pd–C bond eclipsing by phenyl rings deactivates

  通过 2-bromo-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (NN-Br) 与四（三苯基膦）钯 (0) 的相互作用，一种新的顺磁性钯-有机化合物[Pd (NN) (PPh3) 2Br] 合成。其四氢呋喃溶剂化物的晶体结构由 X 射线衍射确定。获得的数据使我们能够预期，苯环有效地覆盖 Pd-C 键会使化合物在与芳基卤化物的交叉偶联反应中失活，并在正常条件下提供高动力学稳定性。磁化学研究表明，在顺磁性 [Pd (NN) (PPh3) 2Br] 的自旋之间存在弱的反铁磁交换相互作用。
• ——
  作者：O. V. Koreneva、G. V. Romanenko、V. N. Ikorskii、S. V. Fokin、V. I. Ovcharenko

  DOI：10.1023/a:1017933803737

  日期：——

  Crystal and molecular structure of the nitroxide 2-cyano-4,4,5,5-tetramethyl-3-oxide-2-imidazoline-1-oxyl it-as studied The nontrivial features of the structure are coplanarity of all atoms of the 2-imidazoline heterocycle and the nitrile group bonded to it and short intermolecular contacts between the nitroxyl O atoms and the C atoms in the 2 position of the heterocycles of the neighboring molecules, actually forming layers in the crystal structure. These data agree with the results of magnetic studies,, which are well approximated by the two-dimensional model, which is a rare occurrence for organic magnets.
• The Cyano Nitronyl Nitroxide Radical: Experimental and Theoretical Evidence for the Fourth Case of the McConnell-I Mechanism
  作者：Catherine Hirel、Dominique Luneau、Jacques Pécaut、Lars Öhrström、Guillaume Bussière、Christian Reber

  DOI：10.1002/1521-3765(20020715)8:14<3157::aid-chem3157>3.0.co;2-f

  日期：2002.7.15

  The nitronyl nitroxide 2-cyano-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (1) crystallises in the tetragonal P (4) over bar2(1)m space group with a = 7.4050(7), c = 8.649(1) Angstrom. In the crystal the molecules form layers parallel to the ab plane in which they are orthogonal to each other. In the layers there are close contacts, 2.953(2) Angstrom, between the NO groups and the bridging carbon atoms of the O-N-C-N-O fragment of neighbouring radicals. The calculated spin density shows a positive population mainly and equally localised on the NO groups and small but significant negative spin densities on the bridging carbon atom and the cyano nitrogen. Absorption spectra show temperature-dependent transitions related to the magnetic behaviour. The temperature dependence of the magnetic susceptibility in the range 2-300 K reveals that couplings between the radicals are antiferromagnetic, and is interpreted by considering a two-dimensional square array of spin S = 1/2 antiferromagnetically coupled (J = -10 cm(-1) and g = 2.01). This is interpreted as an exchange coupling through close contact between positive and negative spin densities in orthogonal orbitals on oxygen and carbon atoms, respectively.