2-(diphenylphosphinoyl)-2-methyl-3,4-dihydro-2H-pyrrole 1-oxide | 916844-29-6

• 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: 2-(diphenylphosphinoyl)-2-methyl-3,4-dihydro-2H-pyrrole 1-oxide
• 英文别名: 5-(diphenylphosphinoyl)-5-methyl-4,5-dihydro-3H-pyrrole N-oxide；2-diphenylphosphinoyl-2-methyl-3,4-dihydro-2H-pyrrole N-oxide；5-(diphenylphosphinoyl)-5-methyl-1-pyrroline N-oxide；DPPMPO；2-diphenylphosphoryl-2-methyl-1-oxido-3,4-dihydropyrrol-1-ium
• CAS: 916844-29-6
• 化学式: C₁₇H₁₈NO₂P
• 分子量: 299.309
• InChiKey: SHTDZZFUBGMWNP-UHFFFAOYSA-N

物化性质

• 沸点：
  502.0±43.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(diphenylphosphinoyl)-2-methyl-3,4-dihydro-2H-pyrrole 1-oxide 在 水 、 氧气 、 二甲基亚砜 作用下， 反应 0.08h， 以Ca. 25 μmol的产率得到DPPMPO-OH
  参考文献：
  名称：

  Reevaluation of Quantitative ESR Spin Trapping Analysis of Hydroxyl Radical by Applying Sonolysis of Water as a Model System

  摘要：

  使用 5,5-二甲基-1-吡咯啉 N-氧化物（DMPO）进行电子自旋共振（ESR）自旋捕获通常用于羟基自由基的定量分析。为了更好地理解这种分析方法，我们研究了 DMPO 与 3,3,5,5-四甲基-1-吡咯啉 N-氧化物（M4PO）和 5-（二苯基膦酰基）-5-甲基-1-吡咯啉 N-氧化物（DPPMPO）相比，羟自由基自旋加合物的形成和衰减动力学。在通过超声溶解水产生羟基自由基的研究中，我们发现：(1) 即使羟基自由基持续产生，DMPO-OH 的形成也是饱和的；(2) 停止超声辐照后，DMPO-OH 的浓度与时间成反比下降，这表明衰减是一个二阶反应。通过光解 H2O2 生成 DMPO-OH 的实验也得到了类似的结果。除 DMPO 外，M4PO 和 DPPMPO 也能捕获羟基自由基，但自旋捕获效率低于 DMPO。此外，M4PO-OH 和 DPPMPO-OH 的衰变速度比 DMPO-OH 快。由此，我们得出结论：DMPO 比 M4PO 和 DPPMPO 更适合用于羟自由基的定量分析，但在解释定量分析结果时必须考虑到与 DMPO-OH 的形成和衰变有关的动力学，尤其是在定量分析大量羟自由基生成时。

  DOI：

  10.1246/bcsj.20100078
• 作为产物：
  描述：

  二苯基氯化膦 在 Oxone 、 氨 、 水 、 碳酸氢钠 作用下， 以 乙醇 、 丙酮 、 乙腈 为溶剂， 生成 2-(diphenylphosphinoyl)-2-methyl-3,4-dihydro-2H-pyrrole 1-oxide
  参考文献：
  名称：

  Spin-Trapping Properties of 5-(Diphenylphosphinoyl)-5-methyl-4,5-dihydro-3H-pyrroleN-Oxide (DPPMDPO)

  摘要：

  通过 ESR 光谱法研究了一种新型自旋捕获试剂 5-（二苯基膦酰基）-5-甲基-4,5-二氢-3H-吡咯 N-氧化物（DPPMDPO）的自旋捕获特性。与 DMPO 和 DEPMPO 相比，DPPMDPO 的速率常数更大。作为超氧化物检测的自旋捕获试剂，DPPMDPO 的效果应该优于 DEPMPO。

  DOI：

  10.1246/bcsj.80.495

文献信息

• Cycloadditions of 3,4-Dihydro-2<i>H</i>-pyrrole<i>N</i>-Oxide with Thioketones and a Selenoketone
  作者：Kosei Shioji、Akio Matsumoto、Masahiko Takao、Yoshimitsu Kurauchi、Toshiyuki Shigetomi、Yoshinobu Yokomori、Kentaro Okuma

  DOI：10.1246/bcsj.80.743

  日期：2007.4.15

  Cycloadditions of 2-diphenylphosphinoyl-2-methyl-3,4-dihydro-2H-pyrrole N-oxide (DPhPMPO), 3,4-dihydro-2H-pyrrole N-oxide having a diphenylphosphinoyl group at the C2 position with thioketones afforded the corresponding 1,4,2-oxathiazolidines. Dissociation constants of these 5-membered ring products were determined. The cycloadducts were stabilized by the diphenylphosphinoyl group. The reaction of

  2-二苯基膦酰基-2-甲基-3,4-二氢-2H-吡咯N-氧化物(DPhPMPO)、在C2位具有二苯基膦酰基的3,4-二氢-2H-吡咯N-氧化物与硫酮的环加成得到相应的 1,4,2-恶噻唑烷。测定了这些 5 元环产物的解离常数。环加合物由二苯基膦酰基团稳定。DPhPMPO与二叔丁基硒酮在微波照射下反应得到相应的硒酰胺。硒酰胺的形成表明 DPhPMPO 与硒酮类似物的环加成也通过相应的 5 元环产物的形成进行。
• ESR analysis of the oxidation reactions of phosphorus-containing nitrone-type spin traps with gold(III) ion
  作者：Akira Nakajima、Emiko Matsuda、Yuto Ueda、Kunihiko Tajima

  DOI：10.1139/v10-033

  日期：2010.6

  Phosphorus-containing cyclic nitrones, such as DEPMPO, CYPMPO, and DPPMPO, were oxidized by hydrogen tetrachloroaurate(III) to DEPMPOX, CYPMPOX, and DPPMPOX with the precipitation of Au(0). The reaction was depressed by the addition of chloride or hydroxide ions. The peculiar pH dependency was observed in DEPMPOX, CYPMPOX, and DPPMPOX formation, which should be caused by the diethoxyphosphoryl group in DEPMPO, the 1,3-propoxy cyclophosphoryl group in CYPMPO, and the diphenylphosphinoyl group in DPPMPO. The oxidation of the nitrones proceeded through the ligand exchange of Cl^– in AuCl₄^– with >N⁺–O^– in nitrone and the nucleophilic addition of the water molecule to the C-2 position in the nitrones, the stepwise intra-molecular transfer of three electrons from the nitrones to Au(III), and the release of the resulting Au(0). The phosphoryl group in the nitrones suppressed the first ligand-exchange interaction by its electronegativity, while the group promoted the electron transfer from the nitrones to Au(III) by its inductive effect.

  DEPMPO 、CYPMPO 和 DPPMPO 等含磷环硝基化合物被四氯金酸氢（III）氧化成 DEPMPOX、CYPMPOX 和 DPPMPOX，并有 Au(0) 沉淀。加入氯离子或氢氧根离子会抑制反应。在 DEPMPOX、CYPMPOX 和 DPPMPOX 的形成过程中观察到了特殊的 pH 依赖性，这应该是由 DEPMPO 中的二乙氧基磷酰基、CYPMPO 中的 1,3-丙氧基环磷酰基和 DPPMPO 中的二苯基膦酰基引起的。腈的氧化作用是通过 AuCl4- 中的 Cl- 与腈中的 >N+-O-进行配体交换，水分子与腈中的 C-2 位发生亲核加成反应，三个电子在分子内从腈逐步转移到 Au(III)，最后释放出 Au(0)。硝基中的磷酰基团通过其电负性抑制了第一次配体交换相互作用，而该基团则通过其感应效应促进了电子从硝基转移到 Au(III)。
• [EN] EPR METHOD FOR FREE RADICALS DETECTION USING AT LEAST TWO DIFFERENT SPIN TRAPPING COMPOUNDS<br/>[FR] PROCÉDÉ RPE POUR LA DÉTECTION DE RADICAUX LIBRES UTILISANT AU MOINS DEUX COMPOSÉS DE PIÉGEAGE DE SPIN DIFFÉRENTS
  申请人：UNIV CATHOLIQUE LOUVAIN

  公开号：WO2013045429A1

  公开（公告）日：2013-04-04

  The present invention provides a method, a kit and their use for free radicals detection and identification in a sample. The method comprising the steps of: reacting said sample with a spin trapping composition, to produce spin adducts of said spin trapping composition and free radicals and detecting said spin adducts by electron paramagnetic resonance (EPR) spectroscopy or electron spin resonance (ESR), thereby obtaining an EPR signal. The method is characterized in that said spin trapping composition comprises at least two different spin trapping compounds.
• Spin-Trapping Properties of 5-(Diphenylphosphinoyl)-5-methyl-4,5-dihydro-3<i>H</i>-pyrrole<i>N</i>-Oxide (DPPMDPO)
  作者：Masahiro Nishizawa、Kosei Shioji、Yoshimitsu Kurauchi、Kentaro Okuma、Masahiro Kohno

  DOI：10.1246/bcsj.80.495

  日期：2007.3.15

  Spin-trapping properties of a novel spin-trapping reagent, 5-(diphenylphosphinoyl)-5-methyl-4,5-dihydro-3H-pyrrole N-oxide (DPPMDPO), were investigated by ESR spectroscopy. DPPMDPO had larger rate constants than DMPO and DEPMPO. DPPMDPO should be better than DEPMPO as a spin-trapping reagent for superoxide detection.

  通过 ESR 光谱法研究了一种新型自旋捕获试剂 5-（二苯基膦酰基）-5-甲基-4,5-二氢-3H-吡咯 N-氧化物（DPPMDPO）的自旋捕获特性。与 DMPO 和 DEPMPO 相比，DPPMDPO 的速率常数更大。作为超氧化物检测的自旋捕获试剂，DPPMDPO 的效果应该优于 DEPMPO。
• Reevaluation of Quantitative ESR Spin Trapping Analysis of Hydroxyl Radical by Applying Sonolysis of Water as a Model System
  作者：Keisuke Nakamura、Taro Kanno、Hiroyo Ikai、Emiko Sato、Takayuki Mokudai、Yoshimi Niwano、Toshihiko Ozawa、Masahiro Kohno

  DOI：10.1246/bcsj.20100078

  日期：2010.9.15

  Electron spin resonance (ESR) spin trapping using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) is commonly applied for quantitative analysis of hydroxyl radical. For better understanding of the analysis, we investigated kinetics related to formation and decay of hydroxyl radical spin adduct of DMPO compared with that of 3,3,5,5-tetramethyl-1-pyrroline N-oxide (M4PO) and 5-(diphenylphosphinoyl)-5-methyl-1-pyrroline N-oxide (DPPMPO). In our study where hydroxyl radical was generated by sonolysis of water, we found that (1) DMPO-OH formation was saturated even though hydroxyl radical was generated continuously and (2) the concentration of DMPO-OH decreased in inverse proportion to time after cessation of ultrasound irradiation, suggesting that the decay is a second-order reaction. Similar results were obtained in an experiment of DMPO-OH generated by photolysis of H2O2. Other than DMPO, M4PO, and DPPMPO also trapped hydroxyl radical but the spin trap efficiency was less than that of DMPO. Furthermore, M4PO-OH and DPPMPO-OH decayed more quickly than DMPO-OH. From this, we conclude that DMPO is more suitable for quantification of hydroxyl radical than M4PO and DPPMPO but results from the quantitative analysis must be interpreted with consideration of the kinetics related to formation and decay of DMPO-OH, especially in quantification of large amount of hydroxyl radical generation.

  使用 5,5-二甲基-1-吡咯啉 N-氧化物（DMPO）进行电子自旋共振（ESR）自旋捕获通常用于羟基自由基的定量分析。为了更好地理解这种分析方法，我们研究了 DMPO 与 3,3,5,5-四甲基-1-吡咯啉 N-氧化物（M4PO）和 5-（二苯基膦酰基）-5-甲基-1-吡咯啉 N-氧化物（DPPMPO）相比，羟自由基自旋加合物的形成和衰减动力学。在通过超声溶解水产生羟基自由基的研究中，我们发现：(1) 即使羟基自由基持续产生，DMPO-OH 的形成也是饱和的；(2) 停止超声辐照后，DMPO-OH 的浓度与时间成反比下降，这表明衰减是一个二阶反应。通过光解 H2O2 生成 DMPO-OH 的实验也得到了类似的结果。除 DMPO 外，M4PO 和 DPPMPO 也能捕获羟基自由基，但自旋捕获效率低于 DMPO。此外，M4PO-OH 和 DPPMPO-OH 的衰变速度比 DMPO-OH 快。由此，我们得出结论：DMPO 比 M4PO 和 DPPMPO 更适合用于羟自由基的定量分析，但在解释定量分析结果时必须考虑到与 DMPO-OH 的形成和衰变有关的动力学，尤其是在定量分析大量羟自由基生成时。