1-hydroxy-5,5-dimethyl-4-phenyl-3-imidazoline 3-oxide | 59570-09-1

• 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-hydroxy-5,5-dimethyl-4-phenyl-3-imidazoline 3-oxide
• 英文别名: 1H-Imidazole, 2,5-dihydro-1-hydroxy-5,5-dimethyl-4-phenyl-, 3-oxide；3-hydroxy-4,4-dimethyl-1-oxido-5-phenyl-2H-imidazol-1-ium
• CAS: 59570-09-1
• 化学式: C₁₁H₁₄N₂O₂
• 分子量: 206.244
• InChiKey: DUFGGHRGHRZDBI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  52.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-hydroxy-5,5-dimethyl-4-phenyl-3-imidazoline 3-oxide 在 lead dioxide 作用下， 以 甲醇 为溶剂， 反应 3.0h， 生成 4,4-dimethyl-5-phenyl-4H-imidazole 1,3-dioxide
  参考文献：
  名称：

  Route to stable nitroxides with alkoxy groups at α- carbon - the derivatives of 2- and 3-imidazolines

  摘要：

  DOI：

  10.1016/s0040-4039(01)80859-5

文献信息

• Interaction of heterocyclic nitrones with organometallic reagents as a method for the synthesis of new types of nitroxides
  作者：Vladimir A. Reznikov、Leonid B. Volodarsky

  DOI：10.1016/s0040-4020(01)81557-x

  日期：1993.1

  The reactions of heterocyclic nitroxides: 3-imidazoline-3-oxides, 2H- (4H)-imidazole mono- and dioxides, dihydropyrazine-1,4-dioxides, with organometallic reagents and subsequent oxidation led to heterocyclic nitroxides of 3-(2)-imidazoline and 3-(2)-imidazoline-3-oxide, dihydropyrazine oxide, monocyclic imidazolidine biradicals and stable acyclic nitroxides with hydrogen at the α-carbon atom.

  杂环氮氧化物的反应：3-咪唑啉-3-氧化物，2H-（4H）-咪唑单和二氧化物，二氢吡嗪-1,4-二氧化物与有机金属试剂的反应以及随后的氧化反应生成3-（2）杂环氮氧化物-咪唑啉和3-（2）-咪唑啉-3-氧化物，二氢吡嗪氧化物，单环咪唑烷双自由基和稳定的无环氮氧化物，氢在α-碳原子处。
• ESR and1H NMR studies of a new class of nitroxyl, nitronylnitroxyl and iminonitroxyl radicals
  作者：V. V. Khramtsov、L. M. Weiner、A. Z. Gogolev、I. A. Grigor'ev、V. F. Starichenko、L. B. Volodarsky

  DOI：10.1002/mrc.1260240304

  日期：1986.3

  A new synthesis of nitronylnitroxyl (NNR), iminonitroxyl (INR) and nitroxyl radicals (NR) is suggested, involving oxidation of 4H-imidazol di-N-oxides with O2 or PbO2 in the presence of nucleophilic reagents. This method allowed the preparation of radicals which could not be synthesized by known procedures. These radicals were studied by ESR and 1H NMR spectroscopy. The hyperfine interaction constants of the NNR were measured and assigned (in some cases radicals containing 15N were used). The influence of protonation and deprotonation of functional groups (OH, NH2) in the NNR on their ESR spectra was investigated and the pK values of these radicals were measured by ESR. Differences between the ESR spectra of two isomeric INR were found, and the structures of these radicals were established by 1H NMR. Changes in spin density delocalization in 3-imidazoline 3-oxide nitroxyl radicals were studied, and the spin density was found to be ‘pushed out’ to the peripheral fragments of these radicals on increasing the number of methoxy groups in the α-position to the N—O. fragment. Hindered rotation around the σ-bond of a bulky substituent in the α-position to the N—O. fragment was detected by ESR. The activation energy of this hindered rotation was ΔE = 30±1.7 kJ mol−1.

  本研究提出了一种新的硝酰硝基（NNR）、亚硝酰硝基（INR）和硝基自由基（NR）的合成方法，包括在亲核试剂存在下用 O2 或 PbO2 氧化 4H-imidazol 二-N-氧化物。这种方法可以制备出已知程序无法合成的自由基。通过 ESR 和 1H NMR 光谱对这些自由基进行了研究。对 NNR 的超频相互作用常数进行了测量和分配（在某些情况下使用了含有 15N 的自由基）。研究了 NNR 中官能团（OH、NH2）的质子化和去质子化对其 ESR 光谱的影响，并通过 ESR 测定了这些自由基的 pK 值。 发现了两种异构体 INR 的 ESR 光谱之间的差异，并通过 1H NMR 确定了这些自由基的结构。研究了 3-imidazoline 3-oxide nitroxyl 自由基中自旋密度分散的变化，发现当 N-O. 片段 α 位置上的甲氧基数量增加时，自旋密度会被 "挤出 "到这些自由基的外围片段。ESR 检测到了 N-O 片段 α 位上的一个大块取代基围绕 σ 键的受阻旋转。这种受阻旋转的活化能为 ΔE = 30±1.7 kJ mol-1。
• Reaction of sterically hindered 1-hydroxy-3-imidazoline 3-oxides with phenyllithium
  作者：V. A. Reznikov、L. B. Volodarsky

  DOI：10.1007/bf00695827

  日期：1994.2

  The reaction of 3-imidazoline 3-oxide derivatives with phenyllithium followed by oxidation affords nitroxyl radicals of the 2-imidazoline or 2-imidazoline 3-oxide series depending on the nature of the substituent in position 2 of the heterocycle.

  3-咪唑啉3-氧化物衍生物与苯基锂的反应随后氧化得到2-咪唑啉或2-咪唑啉3-氧化物系列的硝酰基自由基，这取决于杂环2位取代基的性质。
• Oxidative alkoxylation of 4H-imidazole N-oxides as a new method of synthesis of stable nitroxyl radicals of the 2- and 3-imidazoline series with alkoxy groups at the ?-carbon atom of the radical center
  作者：I. A. Grigor'ev、I. A. Kirilyuk、V. F. Starichenko、L. B. Volodarskii

  DOI：10.1007/bf00978444

  日期：1989.7
• Route to stable nitroxides with alkoxy groups at α- carbon - the derivatives of 2- and 3-imidazolines
  作者：I.A. Grigor'ev、L.B. Volodarsky、V.F. Starichenko、G.I. Shchukin、I.A. Kirilyuk

  DOI：10.1016/s0040-4039(01)80859-5

  日期：1985.1