DMPOx | 32378-00-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: DMPOx
• 英文别名: 5,5-dimethyl-2-pyrrolidone-N-oxyl
• CAS: 32378-00-0
• 化学式: C₆H₁₀NO₂
• 分子量: 128.151
• InChiKey: VBDWPOMKMBEDSS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  9
• 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：
  21.3
• 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 水 、 臭氧 作用下， 以 乙腈 为溶剂， 生成 DMPOx
  参考文献：
  名称：

  臭氧和紫外光照射下羟基自由基对氯化持久性有机污染物的氧化破坏

  摘要：

  我们开发了一种在室温下使用臭氧气体和乙腈（ACN）-水（2：1）作为溶剂在紫外光照射下原位产生羟基自由基氧化破坏有机氯和几种持久性有机污染物（POP）的方法。该方法利用臭氧气体将难以氧化的持久性有机污染物降解为有用且无毒的产品，既环保又有助于修复地球大气层。此外，我们还推导了几种有机氯化合物和污染物的可能降解机制。总体而言，该方法温和、操作友好、高效、经济可行，可用于降解各种有机氯化合物。

  DOI：

  10.1039/d3gc02365f

文献信息

• Electron spin resonance analysis of the oxidation reactions of nitrone type spin traps with gold(III) ion
  作者：Akira Nakajima、Yuto Ueda、Nobuyuki Endoh、Kunihiko Tajima、Keisuke Makino

  DOI：10.1139/v05-132

  日期：2005.8.1

  When cyclic nitrones, such as 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), 4-phenyl-5,5-dimethyl-1- pyrroline-N-oxide (PDMPO), and 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (M4PO) were mixed with hydrogen tetrachloro aurate(III), DMPOX (5,5-dimethyl-1-pyrrolid-2-one-N-oxyl) type free radicals appeared with the precipitation of Au(0). The reaction did not proceed with noncyclic nitrones, such as N-tert-butyl-α-phenyl-nitrone (PBN) and α-(4-pyridyl-1-oxide)-N-tert-butyl-nitrone (POBN). The order of the HAuCl₄ decrease was DMPO > PDMPO > M4PO. The reaction was depressed by the addition of chloride or hydroxide ions. 1-Hydroxy-5,5-dimethyl-1-pyrrolid-2-one (HDMPN), the precursor of DMPOX, was also oxidized to DMPOX by HAuCl₄. Every step of the gold reduction from Au(III) to Au(0) can be used for the oxidation of HDMPN to DMPOX. Based on these and previous results, the reaction was assumed to proceed by the following scheme consisting of a ligand exchange interaction of AuCl₄^– with >N⁺–O^– in DMPO, then nucleophilic addition of a water molecule to DMPO, then the stepwise intramolecular transfer of three electrons from DMPO to Au(III), and finally the precipitation of Au(0). Key words: ESR, nitrone, spin traps, DMPO, DMPOX, gold(III) ion.

  当环状亚硝基化合物，如5,5-二甲基-1-吡咯烷-N-氧化物（DMPO）、4-苯基-5,5-二甲基-1-吡咯烷-N-氧化物（PDMPO）和3,3,5,5-四甲基-1-吡咯烷-N-氧化物（M4PO）与氢四氯合金酸（III）混合时，DMPOX（5,5-二甲基-1-吡咋烷酮-N-氧自由基）型自由基随着Au（0）的沉淀出现。但是，非环状亚硝基化合物，如N-叔丁基-α-苯基亚硝基（PBN）和α-（4-吡啶基-1-氧化物）-N-叔丁基亚硝基（POBN）则不会发生反应。 HAuCl4的降解顺序为DMPO> PDMPO> M4PO。氯离子或氢氧根离子的添加抑制了反应。 DMPOX的前体1-羟基-5,5-二甲基-1-吡咯烷（HDMPN）也被HAuCl4氧化为DMPOX。从Au（III）到Au（0）的每个金还原步骤都可以用于将HDMPN氧化为DMPOX。根据这些和以前的结果，假定该反应通过以下方案进行，包括AuCl4-与DMPO中的>N+-O-的配体交换相互作用，然后是一个水分子对DMPO的亲核加成，然后是从DMPO向Au（III）的逐步分子内转移三个电子，最后是Au（0）的沉淀。关键词：ESR、亚硝基、自旋陷阱、DMPO、DMPOX、金（III）离子。
• Online Quantification of Criegee Intermediates of α-Pinene Ozonolysis by Stabilization with Spin Traps and Proton-Transfer Reaction Mass Spectrometry Detection
  作者：Chiara Giorio、Steven J. Campbell、Maurizio Bruschi、Francesco Tampieri、Antonio Barbon、Antonio Toffoletti、Andrea Tapparo、Claudia Paijens、Andrew J. Wedlake、Peter Grice、Duncan J. Howe、Markus Kalberer

  DOI：10.1021/jacs.6b10981

  日期：2017.3.22

  first-generation products of these reactions, carbonyl oxides (often named Criegee intermediates), is essential in defining the oxidation pathways of organic compounds in the atmosphere but is highly challenging due to the short lifetime of these zwitterions. Here, we report the development of a novel online method to quantify atmospherically relevant Criegee intermediates (CIs) in the gas phase by stabilization

  生物烯烃是大气中最丰富的挥发性有机化合物之一，很容易被臭氧氧化。表征这些反应的第一代产物羰基氧化物（通常称为 Criegee 中间体）的反应性和动力学，对于定义大气中有机化合物的氧化途径至关重要，但由于这些两性离子的寿命很短，因此极具挑战性。在这里，我们报告了一种新的在线方法的开发，该方法通过自旋阱稳定和质子转移反应质谱分析来量化气相中与大气相关的 Criegee 中间体 (CI)。α-蒎烯的臭氧分解已被选为原理验证模型系统。为了明确地确定具有 α-蒎烯 CI 的自旋陷阱加合物的结构，反应在溶液中进行测试，反应产物用高分辨质谱、电子顺磁共振和核磁共振光谱表征。DFT 计算表明，将 Criegee 中间体添加到 DMPO 自旋陷阱中，导致形成六元环加合物，这是通过非常有利的途径发生的，并且产物明显比反应物更稳定，支持实验表征。流量管设置已用于在气相中生成带有 α-蒎烯 CIs 的自旋陷阱加合物。我们证明了具有
• The structure of amidyl radicals. Evidence for the .pi.-electronic ground state and for twist about the acyl-nitrogen bond by electron paramagnetic resonance spectroscopy
  作者：R. Sutcliffe、D. Griller、J. Lessard、K. U. Ingold

  DOI：10.1021/ja00393a021

  日期：1981.2
• Makino, Keisuke; Hagi, Akifumi; Ide, Hiroshi, Canadian Journal of Chemistry, 1992, vol. 70, # 11, p. 2818 - 2827
  作者：Makino, Keisuke、Hagi, Akifumi、Ide, Hiroshi、Murakami, Akira、Nishi, Masatoshi

  DOI：——

  日期：——
• Singlet Oxygen–mediated Hydroxyl Radical Production in the Presence of Phenols: Whether DMPO–·OH Formation Really Indicates Production of ·OH?¶
  作者：Jun-ichi Ueda、Keizo Takeshita、Shigenobu Matsumoto、Kinya Yazaki、Mitsuru Kawaguchi、Toshihiko Ozawa

  DOI：10.1562/0031-8655(2003)077<0165:somhrp>2.0.co;2

  日期：——

  The reaction of singlet oxygen (O-1(2)) generated by ultraviolet-A (UVA)-visible light (lambda > 330 nm) irradiation of air-saturated solutions of hematoporphyrin with phenolic compounds in the presence of a spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), gave an electron spin resonance (ESR) spectrum characteristic of the DMPO-hydroxyl radical spin adduct (DMPO-(OH)-O-.). In contrast, the ESR signal of 5,5-dimethyl-2-pyrrolidone-N-oxyl, an oxidative product of DMPO, was observed in the absence of phenolic compounds. The ESR signal of DMPO-(OH)-O-. decreased in the presence of either a (OH)-O-. scavenger or a quencher of O-1(2) and under anaerobic conditions, whereas it increased depending on the concentration of DMPO. These results indicate both O-1(2) and DMPO-mediated formation of free (OH)-O-. during the reaction. When DMPO was replaced with 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide (DEPMPO), no DEPMPO adduct of oxygen radical species was obtained. This suggests that 102, as an oxidizing agent, reacts little with DEPMPO, in which a strong electron-withdrawing phosphoryl group increases the oxidation potential of DEPMPO compared with DMPO. A linear correlation between the amounts of DMPO-(OH)-O-. generated and the oxidation potentials of phenolic compounds was observed, suggesting that the electron-donating properties of phenolic compounds contribute to the appearance of (OH)-O-.. These observations indicate that O-1(2) reacts first with DMPO, and the resulting DMPO-O-1(2) intermediate is immediately decomposed/reduced to give (OH)-O-.. Phenolic compounds would participate in this reaction as electron donors but would not contribute to the direct conversion of O-1(2) to (OH)-O-.. Furthermore, DEPMPO did not cause the spin-trapping agent-mediated generation of (OH)-O-. like DMPO did.