3-isocyanato-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrole-1-oxyl | 68212-42-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: 3-isocyanato-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrole-1-oxyl
• CAS: 68212-42-0
• 化学式: C₉H₁₃N₂O₂
• 分子量: 181.214
• InChiKey: MSXYOUPDVAWHJH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  33.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-isocyanato-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrole-1-oxyl 在 氨 作用下， 以 环己烷 为溶剂， 以70%的产率得到1-oxyl-3-ureido-2,2,5,5-tetramethyl-3-pyrroline
  参考文献：
  名称：

  Studies of Structure−Activity Relationship of Nitroxide Free Radicals and Their Precursors as Modifiers Against Oxidative Damage

  摘要：

  The protective effects of stable nitroxides, as well as their hydroxylamine and amine precursors, have been tested in Chinese hamster V79 cells subjected to H2O2 exposure at fixed concentration or exposure to ionizing radiation. Cytotoxicity was evaluated by monitoring the viability of the cells assessed by the clonogenic assay. The compounds tested at fixed concentration varied in terms of ring size, oxidation state, and ring substituents. Electrochemical studies were carried out to measure the redox midpoint potentials. The studies show that in the case of protection against H2O2 exposure, the protection was determined by the ring size, oxidation state, and redox midpoint potentials. In general the protection factors followed the order nitroxides > hydroxylamines > amines. Both the six-membered ring nitroxides and substituted five-membered ring nitroxides were efficient protectors. For six-membered ring nitroxides, the compounds exhibiting the lowest midpoint potentials exhibited maximal protection. In the case of X-radiation, nitroxides were the most protective though some hydroxylamines were also efficient. The amines were in some cases found to sensitize the toxicity of aerobic radiation exposure. The protection observed by the nitroxides was not dependent on the ring size. However, the ring substituents had significant influence on the protection. Compounds containing a basic side chain were found to provide enhanced protection. The results in this study suggest that these compounds are novel antioxidants which can provide cytoprotection in mammalian cells against diverse types of oxidative insult and identify structural determinants optimal for protection against individual types of damage.

  DOI：

  10.1021/jm9802160
• 作为产物：
  描述：

  1-oxyl-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrole-3-carbonyl azide 以 正己烷 为溶剂， 生成 3-isocyanato-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrole-1-oxyl
  参考文献：
  名称：

  螺环己烷取代硝酰基双自由基对动态核极化的影响

  摘要：

  螺取代硝酰基双自由基被广泛用作动态核极化（DNP）试剂，这对于生物聚合物研究尤其重要。它们作为偏振剂适用性的主要标准是自旋-自旋交换相互作用参数（J）的值，当使用不同的偶联剂连接自由基部分时，该参数可能会有很大变化。本文描述了一项关于双自由基的研究，其中含有二茂铁-1,1'-二基取代的 1,3-二氮杂环丁烷-2,4-二亚胺偶联剂，该偶联剂以前从未用作 DNP 试剂。我们观察到带有甲基或螺环己烷取代基的双自由基的电子顺磁共振（EPR）光谱之间的温度依赖性存在显着差异，并使用密度泛函理论（DFT）计算结果解释了这种差异。结果表明，NO 基团附近的甲基被螺环取代导致J ≈ 0 的构象异构体的贡献增加。观察到具有甲基取代基的双自由基的 DNP 增益比螺环取代的双自由基高三倍硝酰基双自由基，并且与显示可忽略的交换相互作用的双自由基的贡献成反比。还研究了氮氧双自由基中的亲核基团和取代基对1,3-二氮杂

  DOI：

  10.3390/molecules27103252

文献信息

• Synthesis of N-Substituted 3,5-Bis(arylidene)-4-piperidones with High Antitumor and Antioxidant Activity
  作者：Tamás Kálai、M. Lakshmi Kuppusamy、Mária Balog、Karuppaiyah Selvendiran、Brian K. Rivera、Periannan Kuppusamy、Kálmán Hideg

  DOI：10.1021/jm200353f

  日期：2011.8.11

  A series of 3,5-bis(arylidene)-4-piperidone (DAP) compounds are considered as synthetic analogues of curcumin for anticancer properties. We performed structure–activity relationship studies by synthesizing a number of DAPs N-alkylated or acylated with nitroxides or their amine precursors as potent antioxidant moieties. Both subtituents on arylidene rings and on piperidone nitrogen (five- or six-membered

  一系列3,5-双（亚芳基）-4-哌啶酮（DAP）化合物被认为是姜黄素的合成类似物，具有抗癌作用。我们通过合成大量用氮氧化物或其胺前体作为有效抗氧化剂部分进行了N-烷基化或酰化的DAP，进行了结构-活性关系研究。亚芳基环上和哌啶酮氮上的取代基（五元或六元，2-或3-取代或3,4-二取代的异吲哚啉氮氧化物）都不同。通过测量新的DAP化合物对癌细胞系A2780和MCF-7以及对H9c2细胞系的细胞毒性来测试其抗癌功效。结果表明，所有DAP化合物均可在测试的人类癌细胞系中诱导细胞活力的显着降低。但是，只有吡咯啉附加了一氧化氮（5c（K.Selvendiran；Tong L .; A. Bratasz；LM库普萨米（LM）；艾哈迈德（美国）；拉维（Yavi）；新泽西州特里格; 里维拉（BK）; 卡莱，T。Hideg，K .; 库普萨米（P. Kuppusamy） 大声笑 癌症治疗师。 2010，9，
• A nitroxide diradical containing a ferrocen-1,1′-diyl-substituted 1,3-diazetidine-2,4-diimine coupler
  作者：Irina Bagryanskaya、Matvey Fedin、Dmitry Gorbunov、Nina Gritsan、Larisa Gurskaya、Maxim Kazantsev、Yuliya Polienko、Dmitri Stass、Evgeny Tretyakov

  DOI：10.1016/j.tetlet.2016.12.068

  日期：2017.2

  The two Cp rings are constricted by the 1,3-diazetidine-2,4-diimine moiety so that the angle between their planes is 11.0°. The synthesized diradical contains ferrocene and nitroxide redox signaling units that can be oxidized step-by-step at E1/2 = 0.26 and 0.48 V (vs Fc/Fc+), respectively. Electron spin resonance spectroscopy revealed a moderate exchange interaction (|J| ∼ aN) between the two nitroxide

  1,1'-双（三苯基磷酰苯胺基氨基）二茂铁与3-异氰酸根合-2,2,5,5-四甲基-2,5-二氢-1H-吡咯-1-氧基和随后分子内的Aza-Wittig反应[2双（碳二亚胺）中间体的+2]-环加成用于合成带有两个自由基基团并桥接环戊二烯基（Cp）环的1,3-二氮杂环丁烷-2,4-二亚胺部分。根据单晶X射线数据，平面的2，4-二亚氨基-1，3-二氮杂环丁烷部分相对于偏光的Cp环采用垂直取向。自由基基团中的一个几乎位于四元1,3-二氮杂环丁烷环的平面内，而另一个基团具有构象优选的取向，二面角为±62.3°。两个Cp环被1，3-二氮杂环丁烷2，4-二亚胺部分收缩，使得它们的平面之间的角度为11.0°。1/2分别 为0.26和0.48 V（相对于Fc / Fc +）。电子自旋共振光谱法揭示了两个氮氧自由基基团之间的适度交换相互作用（| J | 〜a N），并得到以下零场分裂参数值：valuesD∣
• Multispin Systems with a Rigid Ferrocene‐1,1′‐diyl‐Substituted 1,3‐Diazetidine‐2,4‐diimine Coupler: A General Approach
  作者：Larisa Yu. Gurskaya、Yuliya F. Polienko、Tatyana V. Rybalova、Nina P. Gritsan、Alexey A. Dmitriev、Maxim S. Kazantsev、Elena V. Zaytseva、Dmitry A. Parkhomenko、Irina V. Beregovaya、Galina A. Zakabluk、Evgeny V. Tretyakov

  DOI：10.1002/ejoc.202101234

  日期：2022.2.18

  A new approach to high-spin molecules with a ferrocenophane core is proposed based on the reaction of intramolecular [2+2]-cycloaddition of ferrocene-1,1′-diyl bis(carbodiimide) derivatives formed by the stepwise reaction of 1,1′-bis(triphenylphosphoranylidenamino)-ferrocene with organic isocyanates. The direction of [2+2]-cycloaddition is controlled by substituents in the isocyanates, thereby offering

  基于1,1逐步反应形成的二茂铁-1,1'-二基双(碳二亚胺)衍生物的分子内[2+2]-环加成反应，提出了一种具有二茂铁核的高自旋分子的新方法。 '-双(三苯基正膦亚基氨基)-二茂铁与有机异氰酸酯。[2+2]-环加成的方向由异氰酸酯中的取代基控制，从而为创建弱耦合双自由基提供了极好的工具。
• First spin-labeled cytisine derivatives
  作者：Yu. F. Polienko、V. I. Vinogradova、Sh. Sh. Sagdullaev、N. D. Abdullaev、Yu. V. Gatilov、I. A. Grigor′ev

  DOI：10.1007/s10600-013-0588-y

  日期：2013.5

  Spin-labeled cytisine derivatives containing stable pyrrolidine and piperidine nitroxyl radicals were synthesized by acylation and alkylation of the secondary amine. Toxicological studies showed that introduction of the nitroxyl group decreased significantly the general toxicity.

  通过仲胺的酰化和烷基化，合成了含有稳定的吡咯烷和哌啶亚硝基的自旋标记胞嘧啶衍生物。毒理学研究表明，亚硝基的引入大大降低了一般毒性。
• Nitroxylcarbamoyl derivatives of 5-fluorouracil
  作者：V. D. Sen'、V. A. Golubev、G. N. Bogdanov

  DOI：10.1007/bf00962123

  日期：1989.10