2-(N-chloroimino)-5,5-dimethylpyrrolidine-1-oxyl radical | 139871-44-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 亚胺内酰胺
• 英文名称: 2-(N-chloroimino)-5,5-dimethylpyrrolidine-1-oxyl radical
• CAS: 139871-44-6
• 化学式: C₆H₁₀ClN₂O
• 分子量: 161.611
• InChiKey: GBVMBJZRKZIRRP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  16.6
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  5,5-二甲基-1-吡咯啉-N-氧化物 在 KH₂PO₄-H₃PO₄-buffer 、 次氯酸 、 氯化铵 作用下， 以 水 为溶剂， 生成 2-(N-chloroimino)-5,5-dimethylpyrrolidine-1-oxyl radical
  参考文献：
  名称：

  Reaction of 5,5-dimethyl-1-pyrroline 1-oxide with hypochlorite-treated ammonia: the structure of a novel N-chloroimine nitroxyl radical

  摘要：

  A novel nitroxyl radical was observed by electron paramagnetic resonance spectroscopy (EPR) of reaction mixtures containing ammonium ion, hypochlorous acid (HOCl), and 5,5-dimethyl-1-pyrroline 1-oxide (DMPO). The structure of this radical was established as 2-(N-chloroimino)-5,5-dimethylpyrrolidine-1-oxyl on the basis of EPR studies of isotopically-labeled compounds, thin-layer chromatography (TLC), and chemical synthesis by an independent route. Incorporation of deuterium into DMPO and solvent stabilized the radical without affecting the multiplicity of the EPR signal. The use of [N-15]ammonium ion gave 2-(N-15-chloroimino)-5,5-dimethylpyrrolidine-1-oxyl radical. Detection of the radical upon TLC was based on its reaction with potassium iodide-starch to give a purple color, consistent with an N-chloroimine functionality. Synthesis of the new nitroxyl radical was accomplished by the Michael reaction of acrylonitrile and 2-nitropropane, catalytic hydrogenation of the Michael product, and reaction of the reduced compound with HOCl. The formation and EPR detection of 2-(N-chloroimino)-5,5-dimethylpyrrolidine-1-oxyl radical may be useful as a sensitive method for detecting hypochlorous acid and ammonium ion in biological systems.

  DOI：

  10.1021/jo00035a021

文献信息

• Mechanistic Studies by Electron Paramagnetic resonance Spectroscopy on the Formation of 2-(N-Chloroimino)-5,5-dimethylpyrrolidine-1-oxyl Radical from 5,5-Dimethyl-1-pyrroline 1-Oxide and Hypochlorite-Treated Ammonia
  作者：B. M. Ratnayake Bandara、Oscar Hinojosa、Carl Bernofsky

  DOI：10.1021/jo00086a013

  日期：1994.4

  Mixtures of ammonium ion (NH4+) or ammonia (NH3), hypochlorous acid (HOCl), and 5,5-dimethyl-1-pyrroline 1-oxide (DMPO) gave the radical 2-(N-chloroimino)-5,5-dimethylpyrrolidin-1-oxyl (1). The first step in the formation of 1 was the reaction of HOCl and NH4+ to provide ammonia chloramines: monochloramine (NH2Cl), dichloramine (NHC2), and trichloramine (NCl3). Chloramine composition and the formation of 1 were dependent on pH, the ratio of NH4+ to HOCl, and, at acidic pH, on the concentration of chloride in the medium. Conditions were chosen to isolate the individual chloramines in solution for further study. NCl3 and DMPO gave 1; however, NHCl2 and NH2Cl required additional oxidants such as HOCl or PbO2 to produce 1. Studies with N-15-labeled chloramines confirmed that NHCl2 and NH2Cl reacted with DMPO to form N-chloro intermediates that yielded 1 upon subsequent oxidation. Light had no effect on the formation of 1, and UV irradiation did not enhance the EPR signal intensity but caused rapid decay, indicating that radical intermediates of ammonia chloramines were not involved. The mechanism of formation of 1 appeared to involve temporary attachment of chloramine Cl to the nitroxide oxygen of DMPO which activated its beta-carbon for nucleophilic addition of the chloramine N. SubsequentN-chlorination and/or dehydrochlorination, depending on the reactive chloramine, would then provide 1. However, nucleophilic addition of H2O to the activated beta-carbon of DMPO was competitive because 5,5-dimethyl-2-hydroxypyrrolidine-1-oxyl (DMPO-OH) or 5,5-dimethyl-2-pyrrolidone-1-oxyl(DMPOX) radicals were sometimes observed as minor products along with 1. Analogous chloroimine radicals were not obtained from the reaction of ammonia chloramines with 3,3,4,4-tetramethyl-1-pyrroline 1-oxide (M(4)PO) and N-tert-butyl-alpha-phenylnitrone (PBN), although their 2-oxo nitroxyl derivatives and hydroxyl adducts were formed as radical products suggesting that nucleophilic addition of H2O was dominant with these nitroxides.
• Reaction of 5,5-dimethyl-1-pyrroline 1-oxide with hypochlorite-treated ammonia: the structure of a novel N-chloroimine nitroxyl radical
  作者：B. M. Ratnayake Bandara、Oscar Hinojosa、Carl Bernofsky

  DOI：10.1021/jo00035a021

  日期：1992.4

  A novel nitroxyl radical was observed by electron paramagnetic resonance spectroscopy (EPR) of reaction mixtures containing ammonium ion, hypochlorous acid (HOCl), and 5,5-dimethyl-1-pyrroline 1-oxide (DMPO). The structure of this radical was established as 2-(N-chloroimino)-5,5-dimethylpyrrolidine-1-oxyl on the basis of EPR studies of isotopically-labeled compounds, thin-layer chromatography (TLC), and chemical synthesis by an independent route. Incorporation of deuterium into DMPO and solvent stabilized the radical without affecting the multiplicity of the EPR signal. The use of [N-15]ammonium ion gave 2-(N-15-chloroimino)-5,5-dimethylpyrrolidine-1-oxyl radical. Detection of the radical upon TLC was based on its reaction with potassium iodide-starch to give a purple color, consistent with an N-chloroimine functionality. Synthesis of the new nitroxyl radical was accomplished by the Michael reaction of acrylonitrile and 2-nitropropane, catalytic hydrogenation of the Michael product, and reaction of the reduced compound with HOCl. The formation and EPR detection of 2-(N-chloroimino)-5,5-dimethylpyrrolidine-1-oxyl radical may be useful as a sensitive method for detecting hypochlorous acid and ammonium ion in biological systems.