para-ethynyl-(4,4,5,5-tetramethyl-4,5-dihydro-1H-3-(N-oxide)-imidazol-1-yloxyl)-phenyl | 124774-74-9

• 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: para-ethynyl-(4,4,5,5-tetramethyl-4,5-dihydro-1H-3-(N-oxide)-imidazol-1-yloxyl)-phenyl
• 英文别名: 2-(4-ethynylphenyl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl 3-oxide；2-(4-ethynylphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 1-oxyl 3-oxide；2-(4-ethynylphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide；2-(4-ethynylphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl；4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl
• CAS: 124774-74-9
• 化学式: C₁₅H₁₉N₂O₂
• 分子量: 259.328
• InChiKey: HXRFLPNCUQZRDN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.14
• 重原子数：
  19.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  49.21
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  para-ethynyl-(4,4,5,5-tetramethyl-4,5-dihydro-1H-3-(N-oxide)-imidazol-1-yloxyl)-phenyl 在 哌啶 、 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 sodium nitrite 作用下， 以 氯仿 、 溶剂黄146 为溶剂， 反应 1.0h， 生成 2,2'-[(buta-1,3-diyne-1,4-diyl)-di-p-phenylene]-bis(4,4,5,5-tetramethyl-2-imidazoline-1-oxyl)
  参考文献：
  名称：

  摘要：

  2-(Arylylethynylphenyl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl 3-oxides 12 and 13 were synthesized by cross-coupling of aryl iodides with 1-alkynes containing the 4,4,5,5-tetramethyl-2-imidazoline- 1-oxyl 3-oxide fragment. A procedure was developed for the preparation of 3- and 4-ethynylbenzaldehydes with the use of 2-methylbut-3-yn-2-ol.

  DOI：

  10.1023/a:1015026200647
• 作为产物：
  描述：

  4,4,5,5-四甲基-2-{4-[(三甲基甲硅烷基)乙炔基]苯基}咪唑烷-1,3-二醇 在 lead dioxide 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以94%的产率得到para-ethynyl-(4,4,5,5-tetramethyl-4,5-dihydro-1H-3-(N-oxide)-imidazol-1-yloxyl)-phenyl
  参考文献：
  名称：

  Me3Si-取代的咪唑烷-1,3-二醇与 PbO2 的级联反应，包括相应二醇的氧化和随后三甲基甲硅烷基片段的消除

  摘要：

  发现 2-Me3Si-R-取代的（Si-C-sp 或 Si-C-sp(2)）咪唑烷-1,3-二醇与甲醇中的 PbO2 的反应是级联反应，涉及咪唑烷的氧化- 1,3-二醇转化为硝酰基氮氧化物 (NN-R-SiMe3) 并进一步消除 Me3Si 基团以得到 NN-RH。通过参考 2-ethynyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1 的合成证明了一锅法合成硝酰基氮氧化物的效率-oxyl (2), 2-(4-ethynylphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (8), (E)-4 ,4,5,5-四甲基-2-[2-(pyrrolidin-1-yl)vinyl]-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl

  DOI：

  10.1002/ejoc.200700113

文献信息

• Spin Exchange Interaction through Phenylene-Ethynylene Bridge in Diradicals Based on Iminonitroxide and Nitronylnitroxide Radical Derivatives. 1. Experimental Investigation of the Through-Bond Spin Exchange Coupling
  作者：Pascale Wautelet、Jacques Le Moigne、Vladimira Videva、Philippe Turek

  DOI：10.1021/jo034723n

  日期：2003.10.1

  pi-conjugation on the intramolecular through-bond spin coupling have been investigated by changing the length of the spacer within linear derivatives. The EPR studies demonstrate the intramolecular magnetic coupling between the radical spins within all compounds. This result is very attractive and unusual, given the large distance between the radicals from 15 A in the dimer to 36 A in the pentamer.

  已经制备了一系列不同长度和几何形状的双亚氨基硝基二自由基衍生物，它们结合了共轭亚苯基-亚乙炔基桥作为刚性间隔基。本文介绍了这些新组件的合成及其主要特征。对于取代的“间亚苯基”基双自由基，发现了意外的单重态基态和取代基对单重态-三重态间隙的影响。通过改变线性导数内间隔基的长度，研究了π共轭对分子内通过键的自旋偶合的影响。EPR研究表明，所有化合物中自由基自旋之间的分子内磁耦合。鉴于自由基之间的距离（二聚体中的15 A与五聚体中的36 A之间的距离较大），因此此结果非常诱人且不寻常。
• Dual Dopable Poly(phenylacetylene) with Nitronyl Nitroxide Pendants for Reversible Ambipolar Charging and Discharging
  作者：Kenichi Oyaizu、Takashi Sukegawa、Hiroyuki Nishide

  DOI：10.1246/cl.2011.184

  日期：2011.2.5

  An electrode-attached layer of poly(phenylacetylene) bearing a pendant nitronyl nitroxide group per repeating unit, obtained by the Rh-catalyzed polymerization of 2-(4-ethynylphenyl)-4,4,5,5-tetramethylimidazoline-l-oxyl 3-oxide, underwent oxidation and reduction at 0.80 and −0.84 V vs. Ag/AgCl, respectively. The magnetically determined unpaired electron density of 92% was coulometrically reproduced, which supported the presumption that the radical survived during the course of the polymerization to allow both positive and negative charging of the pristine neutral polymer substantially per repeating unit. Galvanostatic Coulomb titration revealed the charge storage capability of the polymer, which demonstrated usefulness as organic electrode-active material with unprecedented ambipolar chargeability.

  通过 Rh 催化聚合 2-(4-乙炔基苯基)-4,4,5,5-四甲基咪唑啉-l-氧 3-氧化物，在 0.80V 和 -0.84V 电压下分别与 Ag/AgCl 发生氧化和还原反应。经磁力测定的非配对电子密度（92%）通过库仑计法得以重现，这支持了这样一种推测，即自由基在聚合过程中存活下来，从而使原始中性聚合物的每个重复单元都能产生大量的正负电荷。电静态库仑滴定法显示了这种聚合物的电荷存储能力，证明了其作为有机电活性材料的实用性，具有前所未有的两极带电能力。
• NCN Pincer–Pt Complexes Coordinated by (Nitronyl Nitroxide)-2-ide Radical Anion
  作者：Xun Zhang、Shuichi Suzuki、Masatoshi Kozaki、Keiji Okada

  DOI：10.1021/ja308103g

  日期：2012.10.31

  New pincer-Pt complexes coordinated by (nitronyl nitroxide)-2-ide radical anion were prepared as stable compounds in high yields. The structures of these Pt complexes and the oxidized complexes were unequivocally determined by spectral and crystal structure analyses. The oxidation potential of the nitronyl nitroxide moiety in these complexes was shifted in the negative direction by ~0.6 V as a result

  以高产率制备了由 (硝基氮氧)-2-ide 自由基阴离子配位的新型钳形-Pt 配合物作为稳定化合物。这些 Pt 配合物和氧化配合物的结构通过光谱和晶体结构分析明确确定。由于与 Pt(II) 原子配位，这些配合物中硝酰基氮氧化合物部分的氧化电位向负方向移动了 ~0.6 V。
• Ruthenium Carbon-Rich Complexes as Redox Switchable Metal Coupling Units
  作者：Emmanuel Di Piazza、Areej Merhi、Lucie Norel、Sylvie Choua、Philippe Turek、Stéphane Rigaut

  DOI：10.1021/acs.inorgchem.5b00667

  日期：2015.7.6

  magnetic coupling between two organic radicals R, i.e., two nitronyl nitroxide or two verdazyl units, which is stronger than that of related platinum organometallic systems. Surprisingly, further oxidation of the ruthenium redox-active metal coupling unit (MCU), which introduces an additional spin unit on the carbon-rich part, leads to the switching off of this interaction. On the contrary, in simpler complexes

  借助EPR光谱，我们表明抗磁性[Ru（dppe）2（-C≡C-R）2 ]系统在两个有机基团R（即两个硝酰基硝基氧或两个Verdazyl单元）之间建立了磁耦合，它比相关的铂有机金属体系强。出乎意料的是，钌氧化还原-活性金属偶联单元（MCU）的进一步氧化，在富碳部分上引入了额外的自旋单元，导致这种相互作用的中断。相反，在仅带有一种有机自由基配体的简单络合物中[C 6 H 5 -C≡C-Ru（dppe）2-C≡CR]，过渡金属单元的单电子氧化在两个自旋载流子之间产生了与上述相应中性系统中观察到的相当的相互作用。
• Synthesis and properties of paramagnetic derivatives of linear and fused polyaromatic compounds
  作者：E. V. Tretyakov、T. V. Novikova、V. V. Korolev、O. M. Usov、S. F. Vasilevsky、Yu. N. Molin

  DOI：10.1007/bf02495088

  日期：2000.8

  is an aromatic group, R• is a stable radical center, and Sp is a spacer, were synthesized. The electronic absorption and luminescence spectra of these compounds were examined. The introduction of the paramagnetic dihydroimidazole fragment causes a decrease (10–500-fold) in the quantum yield of luminescence compared to emission of the individual aromatic luminophore. The presence of a radical center

  合成了 A-Sp-R• 类型的甲苯、蒽和三联苯的顺磁性衍生物，其中 A 是芳族基团，R• 是稳定的自由基中心，Sp 是间隔基。检查了这些化合物的电子吸收和发光光谱。与单个芳香族发光体的发射相比，顺磁性二氢咪唑片段的引入导致发光量子产率降低（10-500 倍）。（烷烃）•+/-•A-Sp-R• 自由基-离子对中自由基中心 (R•) 的存在导致在重组时产生的发光磁效应消失或快速（纳秒）衰减这些对。