bis-TEMPO-bisketal | 68491-47-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂螺癸烷衍生物
• 英文名称: bis-TEMPO-bisketal
• 英文别名: bTbk
• CAS: 68491-47-4
• 化学式: C₂₃H₄₀N₂O₆
• 分子量: 440.58
• InChiKey: JROVVEOLMNRDDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  31
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  83.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  bis-TEMPO-bisketal 、 cucurbit[8]uril 以 水 为溶剂， 生成 C₄₈H₄₈N₃₂O₁₆*C₂₃H₄₀N₂O₆
  参考文献：
  名称：

  EPR 光谱：分析超分子宿主•客体与葫芦脲稳定自由基复合物的强大工具

  摘要：

  由于单电子赋予的多重和不寻常的特性，稳定的有机自由基成为越来越多的研究化合物。然而，作为顺磁性，经典方法如核磁共振光谱由于弛豫和线展宽效应而难以使用。EPR 光谱因此更适合获取有关单个电子的直接环境的信息。EPR 能够在主客体化学的背景下获得有用的数据，这里报告了一个经典的例子，用于稳定的 (2,2,6,6-四甲基-4-氧代-哌啶-1-基)氧基或 4-大环宿主葫芦 [7] 脲 (CB[7]) 内的氧代-TEMPO 氮氧化物 (TEMPONE)。一般来说，也在这里观察到，由于宿主疏水腔中的包合物络合导致氮偶联常数降低，因此观察到光谱收缩。与 TEMPO 与 CB[7] 相比，EPR 光谱的模拟允许确定相应的结合常数，表明对 CB[7] 的亲和力较弱。我们通过双自由基的 EPR 光谱结果补充了这项工作：bis-TEMPO-bis-ketal (bTbk) with cucurbit[8]uril

  DOI：

  10.3390/molecules25040776
• 作为产物：
  描述：

  2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tetraoxa-3,15-diaza-trispiro[5.2.2.5.2.2]heneicosane 在 sodium tungstate (VI) dihydrate 、 双氧水 作用下， 以 甲醇 、 水 为溶剂， 反应 24.25h， 以54%的产率得到bis-TEMPO-bisketal
  参考文献：
  名称：

  通过动态核极化增强的15N和29Si NMR光谱了解氮化纤维二氧化硅（KCC-1）纳米催化剂的催化活性

  摘要：

  纤维状纳米二氧化硅（KCC-1）氮氧化物是有前途的固体碱催化剂。矛盾的是，当它们的氮含量增加时，它们的催化活性下降。首次使用动态核极化增强的15 N固态NMR光谱解释了这种违反直觉的观察结果。

  DOI：

  10.1002/anie.201406463

文献信息

• DINITROXIDE-TYPE BIRADICAL COMPOUNDS OPTIMIZED FOR DYNAMIC NUCLEAR POLARIZATION (DNP)
  申请人：OUARI Olivier

  公开号：US20100249386A1

  公开（公告）日：2010-09-30

  The present invention relates to the field of organic chemistry and in particular to organic free radicals used as polarizing agents in the technique of Dynamic Nuclear Polarization (DNP), which involves transferring the polarization of electron spins to the nuclei of a compound whose Nuclear Magnetic Resonance (NMR) is being observed. It concerns dinitroxide-type biradical polarizing agents characterized by a rigid linkage between the nitroxide units that enables optimal orientation and distance to be maintained between the aminoxyl groups of said nitroxide units. This particular structure enables, at low temperatures and high fields, optimal transfer of polarization and optimal enhancement of NMR/MAS signals of the polarized nuclei of the compound studied.

  本发明涉及有机化学领域，特别是有机自由基作为极化剂在动态核极化（DNP）技术中的应用，该技术涉及将电子自旋的极化转移到正在观察的化合物的核磁共振（NMR）中。它涉及一种二硝基型双自由基极化剂，其特点是硝基单元之间具有刚性连接，使得硝基单元的氨氧基之间的最佳定向和距离得以保持。这种特殊结构在低温和高场下，使得被研究化合物的极化核的极化转移和NMR/MAS信号的最佳增强得以实现。
• Organic multishell isostructural host–guest crystals: fullerenes C60 inside a nitroxide open framework
  作者：David Bardelang、Michel Giorgi、Cédric Pardanaud、Virginie Hornebecq、Egon Rizzato、Paul Tordo、Olivier Ouari

  DOI：10.1039/c3cc00170a

  日期：——

  The dinitroxide biradical bTbk crystallizes forming hexagonal open frameworks with one-dimensional corrugated channels filled with crystallization solvent. The large pockets constitutive of the channels allowed the inclusion of C60 in the paramagnetic network. The rapidity and high fidelity of crystal growth were used to prepare isostructural multilayer host–guest crystals successively stained with C60.

  二亚硝基双拉德bTbk结晶后形成六边形开放式框架，并带有充满结晶溶剂的一维波纹通道。通道中形成的大口袋允许顺磁网络中加入 C60。利用晶体生长的快速性和高保真性，制备出了连续沾有 C60 的等结构多层主客晶体。
• Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K
  作者：Alexandre Zagdoun、Gilles Casano、Olivier Ouari、Martin Schwarzwälder、Aaron J. Rossini、Fabien Aussenac、Maxim Yulikov、Gunnar Jeschke、Christophe Copéret、Anne Lesage、Paul Tordo、Lyndon Emsley

  DOI：10.1021/ja405813t

  日期：2013.8.28

  A series of seven functionalized nitroxide biradicals (the bTbK biradical and six derivatives) are investigated as exogenous polarization sources for dynamic nuclear polarization (DNP) solid-state NMR at 9.4 T and with ca. 100 K sample temperatures. The impact of electron relaxation times on the DNP enhancement (epsilon) is examined, and we observe that longer inversion recovery and phase memory relaxation times provide larger E. All radicals are tested in both bulk 1,1,2,2-tetrachloroethane solutions and in mesoporous materials, and the difference in E between the two cases is discussed. The impact of the sample temperature and magic angle spinning frequency on epsilon is investigated for several radicals each characterized by a range of electron relaxation times. In particular, TEKPol, a bulky derivative of bTbK with a molecular weight of 905 g.mol(-1), is presented. Its high-saturation factor makes it a very efficient polarizing agent for DNP, yielding unprecedented proton enhancements of over 200 in both bulk and materials samples at 9.4 T and 100 K. TEKPol also yields encouraging enhancements of 33 at 180 K and 12 at 200 K, suggesting that with the continued improvement of radicals large e may be obtained at higher temperatures.
• Insights into the Catalytic Activity of Nitridated Fibrous Silica (KCC-1) Nanocatalysts from¹⁵N and²⁹Si NMR Spectroscopy Enhanced by Dynamic Nuclear Polarization
  作者：Aany Sofia Lilly Thankamony、Cédric Lion、Frédérique Pourpoint、Baljeet Singh、Angel J. Perez Linde、Diego Carnevale、Geoffrey Bodenhausen、Hervé Vezin、Olivier Lafon、Vivek Polshettiwar

  DOI：10.1002/anie.201406463

  日期：2015.2.9

  Fibrous nanosilica (KCC‐1) oxynitrides are promising solid‐base catalysts. Paradoxically, when their nitrogen content increases, their catalytic activity decreases. This counterintuitive observation is explained here for the first time using 15N‐solid‐state NMR spectroscopy enhanced by dynamic nuclear polarization.

  纤维状纳米二氧化硅（KCC-1）氮氧化物是有前途的固体碱催化剂。矛盾的是，当它们的氮含量增加时，它们的催化活性下降。首次使用动态核极化增强的15 N固态NMR光谱解释了这种违反直觉的观察结果。
• EPR Spectroscopy: A Powerful Tool to Analyze Supramolecular Host•Guest Complexes of Stable Radicals with Cucurbiturils
  作者：Fengbo Liu、Hakim Karoui、Antal Rockenbauer、Simin Liu、Olivier Ouari、David Bardelang

  DOI：10.3390/molecules25040776

  日期：——

  reported here for the stable (2,2,6,6-tetramethyl-4-oxo-piperidin-1-yl)oxyl or 4-oxo-TEMPO nitroxide (TEMPONE) inside the macrocycle host cucurbit[7]uril (CB[7]). Generally and also observed here, a contraction of the spectrum is observed as a result of the reduced nitrogen coupling constant due to inclusion complexation in the hydrophobic cavity of the host. Simulations of EPR spectra allowed determining

  由于单电子赋予的多重和不寻常的特性，稳定的有机自由基成为越来越多的研究化合物。然而，作为顺磁性，经典方法如核磁共振光谱由于弛豫和线展宽效应而难以使用。EPR 光谱因此更适合获取有关单个电子的直接环境的信息。EPR 能够在主客体化学的背景下获得有用的数据，这里报告了一个经典的例子，用于稳定的 (2,2,6,6-四甲基-4-氧代-哌啶-1-基)氧基或 4-大环宿主葫芦 [7] 脲 (CB[7]) 内的氧代-TEMPO 氮氧化物 (TEMPONE)。一般来说，也在这里观察到，由于宿主疏水腔中的包合物络合导致氮偶联常数降低，因此观察到光谱收缩。与 TEMPO 与 CB[7] 相比，EPR 光谱的模拟允许确定相应的结合常数，表明对 CB[7] 的亲和力较弱。我们通过双自由基的 EPR 光谱结果补充了这项工作：bis-TEMPO-bis-ketal (bTbk) with cucurbit[8]uril