1,3-Bis(4',4',5',5'-tetramethylimidazolin-2'-yl)benzene-1'.1''-dioxide-3',3''-dioxyl | 38577-45-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,3-Bis(4',4',5',5'-tetramethylimidazolin-2'-yl)benzene-1'.1''-dioxide-3',3''-dioxyl
• 英文别名: 1,3-Bis(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)benzene；1,3-bis(4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl-2yl)benzene；1,3-bis(1-oxyl-3-oxido-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-2-yl)benzene；1,3-bis-(1'-oxyl-3'-oxido-4',4',5',5'-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene；NITmbis
• CAS: 38577-45-6
• 化学式: C₂₀H₂₈N₄O₄
• 分子量: 388.467
• InChiKey: PAGQTGPIISLFQN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  66
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,3-Bis(4',4',5',5'-tetramethylimidazolin-2'-yl)benzene-1'.1''-dioxide-3',3''-dioxyl 在 盐酸 、 sodium nitrite 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以74%的产率得到1,3-Bis(1-oxyl-4,4,5,5-tetramethylimidazolin-2-yl)benzene
  参考文献：
  名称：

  Towards a Better Understanding of the Magnetic Interactions withinm-Phenyleneα-Nitronyl Imino Nitroxide Based Biradicals

  摘要：

  An extensive investigation of the magnetic properties of three series of biradicals (bis-nitronyl nitroxides diNN-R, bis-imino nitroxides diIN-R and mixed INNN-R. where R is either hydrogen, a triple bond or trimethylsilylacetylenic group) has been carried out to give clear values of the intramolecular interactions through the m-phenylene coupling unit with alpha -nitronyl nitroxides (NN) or alpha -imino nitroxides (IN). An EPR study of the molecules in the isolated state is validated by ab initio calculations, which show the respective influence of spin polarisation and molecular conformation on the singlet-triplet gaps. All these results indicate that the triplet state is the ground state for such biradicals. except when the imidazolyl cycles are orthogonal to the phenyl ring. The magnetic properties of the biradicals in the solid state can be rationalised by examination of the short contacts produced between the ONC-NO and ONCN groups. EPR studies on single crystals of the H-substituted series have confirmed the presence of a structural distortion for diNN-H whereas diIN-H and INNN-H do not exhibit such a peculiarity. The magnetic behav lour of diIN-H is described well by a four-spins model, with a strong intermolecular antiferromagnetic interaction of -90 K, whereas in the case of the two other compounds. a supplementary contact involves more complex interactions between the dimers. The compound diNN-tmsa exhibits a ferromagnetic intermolecular interaction of +11 K within the dimers, and this could be attributed to the relative disposition of the imidazolyl rings. Compound diNN-tr reveals a chain-like behaviour, whereas diIN-tr shows a predominant antiferromagnetic interaction within the dimers. The values for the intramolecular interactions in the solid state are in good agreement with those found for the isolated molecules.

  DOI：

  10.1002/1521-3765(20010601)7:11<2466::aid-chem24660>3.0.co;2-4
• 作为产物：
  描述：

  2,3-二甲基-2,3-二硝基丁烷 在 sodium periodate 、 氯化铵 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 生成 1,3-Bis(4',4',5',5'-tetramethylimidazolin-2'-yl)benzene-1'.1''-dioxide-3',3''-dioxyl
  参考文献：
  名称：

  硝酰基硝基氧双自由基配位的铜（II）配合物的合成，晶体结构和磁性

  摘要：

  由硝化基氮氧化物双自由基NITPh（3-NIT）和Cu II（hfac）2（H 2 O）2构件[NITPh（3-NIT）= 1,3-bis（1'-oxyl-3）构建的配位化合物成功合成了'-oxido-4'，4'，5'，5'-四甲基-4,5-二氢-1 H-咪唑-2-y1）-苯，hfac =六氟乙酰丙酮]。晶体结构通过X射线单晶衍射确定。不对称络合物{[（（NITPh（3-NIT）] Cu（hfac）2）由一个Cu（II）离子和两个> N–O •基团组成，并采用具有五配位中心铜（II）的扭曲三角双锥体）原子和三个hfac氧原子在碱基处，且> N–O •末端有一个氧原子和一个hfac氧原子。分子内O 在分子之间观察到.O键和π–π堆积相互作用。对配位化合物的磁化率研究表明，Cu（II）离子与> N–O •基团之间存在反铁磁相互作用，Cu（II）离子与自由的> N–O •基团之间通过O.产生的铁

  DOI：

  10.1177/1747519820982539

文献信息

• Radical Metalloids with <i>N</i>-Heterocyclic Carbene and Phenanthroline Ligands: Synthesis, Properties, and Cross-Coupling Reaction of [(Nitronyl Nitroxide)-2-ido]metal Complexes with Aryl Halides
  作者：Kiyomi Yamada、Xun Zhang、Ryu Tanimoto、Shuichi Suzuki、Masatoshi Kozaki、Rika Tanaka、Keiji Okada

  DOI：10.1246/bcsj.20180033

  日期：2018.7.15

  New radical metalloids, NN-AuSIMes and NN-Cu(bdmpphen), were prepared and their properties were investigated. They were applied to Pd(0)-mediated cross-coupling reactions with aryl halides (ArX) to produce 2-aryl (nitronyl nitroxide)s in moderate to high yields.

  制备了新的自由基类金属，NN-AuSIMes 和 NN-Cu(bdmpphen)，并研究了它们的性质。它们被应用于 Pd(0) 介导的与芳基卤化物 (ArX) 的交叉偶联反应，以中等至高产率生产 2-芳基（硝基硝基氧）。
• Nitronyl Nitroxide as a Coupling Partner: Pd-Mediated Cross-coupling of (Nitronyl nitroxide-2-ido)(triphenylphosphine)gold(I) with Aryl Halides
  作者：Ryu Tanimoto、Shuichi Suzuki、Masatoshi Kozaki、Keiji Okada

  DOI：10.1246/cl.131162

  日期：2014.5.5

  A cross-coupling reaction using nitronyl nitroxide (NN) as a coupling partner was developed: Refluxing a mixture of [AuI(NN-2-ido)(PPh3)] and aryl iodide (Ar–I) in THF in the presence of 10 mol % [Pd(PPh3)4] produced a cross-coupling product NN-Ar in a high yield. This method allowed the direct introduction of the NN radical onto various poly- and heterocyclic aromatic rings.

  开发了一种使用硝酮亚硝基（NN）作为偶联伙伴的交叉偶联反应：将[AuI(NN-2-ido)(PPh3)]和芳基碘（Ar–I）的混合物在THF中回流，并加入10 mol %的[Pd(PPh3)4]，可以高产率地生成交叉偶联产物NN-Ar。该方法允许将NN自由基直接引入各种多环和杂环芳香环。
• A Family of Homologous Heterospin Complexes Based on Lanthanides and Biradical Ligands
  作者：Li Tian、Ya‐Qiu Sun、Bo Na、Peng Cheng

  DOI：10.1002/ejic.201300524

  日期：2013.8.12

  three spin complexes, in which a NITPhmbis molecule acts as a bidentate ligand with one coordinated lanthanide ion. The four complexes are isomorphous, the coordination number around the lanthanide ion is eight, and the polyhedron is a 4,4-bicappped trigonal prism. For lanthanum(III) complex 1, the temperature dependence of the magnetic susceptibility indicates that weakly antiferromagnetically coupled

  四种基于稀土双自由基的配合物 [Ln(hfac)3(NITPhmbis)2]2 Ln = La (1), Nd (2), Gd (3), Tb (4); hfac = 六氟乙酰丙酮；NITPhmbis = [1,3-bis(1'-oxyl-3'-oxido-4',4',5',5'-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzo]}在合适的条件下合成成功。单晶结构表明，1 是单核二自旋配合物，2-4 是单核三自旋配合物，其中 NITPhmbis 分子作为双齿配体与一个配位的镧系元素离子。四个配合物同晶，镧系离子周围的配位数为8，多面体为4,4-二头三棱柱。对于镧 (III) 配合物 1，磁化率的温度依赖性表明存在弱反铁磁耦合自由基（Jrad-rad = –1.2 cm-1）。在钕 (III) 配合物 2 的情况下，其磁性行为提供了反铁磁 NdIII
• Single molecule magnet behaviour in robust dysprosium–biradical complexes
  作者：Kevin Bernot、Fabrice Pointillart、Patrick Rosa、Mael Etienne、Roberta Sessoli、Dante Gatteschi

  DOI：10.1039/c0cc00966k

  日期：——

  A Dy–biradical complex was synthesized and characterized down to very low temperature. ac magnetic measurements reveal single molecule magnet behaviour visible without any application of dc field. The transition to the quantum tunneling regime is evidenced. Photophysical and EPR measurements provide evidence of the excellent stability of these complexes in solution.

  在极低温度下合成并表征了Dy-双自由基复合物。交流磁测量显示，无需施加直流电场即可观察到单分子磁体的行为。量子隧道效应的过渡得到了证实。光物理和EPR测量证明了这些复合物在溶液中的优异稳定性。
• Caneshi, Andrea; Gatteschi, Dante; Rentschler, Eva, Gazzetta Chimica Italiana, 1995, vol. 125, # 6, p. 283 - 286
  作者：Caneshi, Andrea、Gatteschi, Dante、Rentschler, Eva、Sessoli, Roberta

  DOI：——

  日期：——