2-methyl-2-(2-oxo-1,3,2-dioxaphosphinan-2-yl)pyrrolidine | 902503-50-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: 2-methyl-2-(2-oxo-1,3,2-dioxaphosphinan-2-yl)pyrrolidine
• 英文别名: 2-(2-Methylpyrrolidin-2-yl)-1,3,2lambda5-dioxaphosphinane 2-oxide；2-(2-methylpyrrolidin-2-yl)-1,3,2λ5-dioxaphosphinane 2-oxide
• CAS: 902503-50-8
• 化学式: C₈H₁₆NO₃P
• 分子量: 205.194
• InChiKey: HXWKIBUMAADALB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-methyl-2-(2-oxo-1,3,2-dioxaphosphinan-2-yl)pyrrolidine 在 sodium tungstate 、 双氧水 作用下， 以 水 为溶剂， 反应 48.0h， 以90%的产率得到2-methyl-2-(2-oxo-1,3,2-dioxaphosphinan-2-yl)-3,4-dihydro-2H-pyrrole 1-oxide
  参考文献：
  名称：

  CyDEPMPOs: A class of stable cyclic DEPMPO derivatives with improved properties as mechanistic markers of stereoselective hydroxyl radical adduct formation in biological systems

  摘要：

  The cis/trans diastereoisomeric composition of hydroxyl radical adducts to chiral cyclic nitrones can be used to approach mechanisms of free radical formation in biological systems. Such determination is greatly simplified when both diastereoisomers have ESR spectra with at least two non-overlapping lines. To achieve this prerequisite, a series of DEPMPO-derived spin traps bearing one unsubstituted or alkyl-substituted 2-oxo-1,3,2-dioxaphosphorinane ring were synthesized and their structures were confirmed by X-ray diffraction, H-1, C-13 and P-31 NMR. These CyDEPMPOs nitrones showed variable lipophilicities and LD50 values on murine fibroblasts compatible with a safe use in biological spin trapping. All CyDEPMPOs formed persistent spin adducts with a series of free radicals, including superoxide and hydroxyl (i.e., CyDEPMPOs-OH) and the in vitro half-life times of these two latter were at least as extended as those of parent DEPMPO. Using four methods of CyDEPMPOs-OH formation, the cis-CyDEPMPOs-OH percentage was found significantly varied with substitution on the P-containing ring and, more interestingly, with the generating system. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2011.02.040
• 作为产物：
  描述：

  2-甲基吡咯啉 、 1,3,2-二氧杂磷杂环己烷-2-氧化物 以 甲苯 为溶剂， 以52%的产率得到2-methyl-2-(2-oxo-1,3,2-dioxaphosphinan-2-yl)pyrrolidine
  参考文献：
  名称：

  具有近中性 pKa 的新型空间拥挤和构象受限的 α-氨基膦酸盐作为高精度 31P NMR pH 探针。盘基网柄菌细胞微妙 pH 梯度测定的应用

  摘要：

  为了发现新的31 P NMR 标记物用于探测生物环境中的细微 pH 变化（<0.2 pH 单位），合成了 15 种新的构象受限或空间位阻的 α-氨基膦酸盐，它们源自二乙基（2-甲基吡咯烷-2-基）膦酸盐，并测试了它们的 pH 值报告和体外细胞毒性。所有化合物均显示出接近中性的 p K a s（范围为 6.28–6.97）、与磷代谢物不重叠的化学位移和光谱灵敏度（即化学位移变化 Δ δ ab介于酸性和碱性形式之间）范围为 9.2-10.7 ppm，比传统的内源性标记物（如无机磷酸盐）大四倍。X 射线晶体学研究与预测性经验关系和从头计算相结合，解决了与质子化胺功能相关的取代基的诱导和立体化学效应。在 p K a s 与二维结构和磷的金字塔化之间建立了令人满意的相关性，表明磷周围的空间拥挤对于调节 Δ δ ab至关重要。最后，命中31 P NMR pH 探针1b带有未取代的 1,3,2-二氧杂磷环烷环，它具有中等亲脂性，对

  DOI：

  10.3390/molecules27144506

文献信息

• CyDEPMPOs: A class of stable cyclic DEPMPO derivatives with improved properties as mechanistic markers of stereoselective hydroxyl radical adduct formation in biological systems
  作者：Gaëlle Gosset、Jean-Louis Clément、Marcel Culcasi、Antal Rockenbauer、Sylvia Pietri

  DOI：10.1016/j.bmc.2011.02.040

  日期：2011.4

  The cis/trans diastereoisomeric composition of hydroxyl radical adducts to chiral cyclic nitrones can be used to approach mechanisms of free radical formation in biological systems. Such determination is greatly simplified when both diastereoisomers have ESR spectra with at least two non-overlapping lines. To achieve this prerequisite, a series of DEPMPO-derived spin traps bearing one unsubstituted or alkyl-substituted 2-oxo-1,3,2-dioxaphosphorinane ring were synthesized and their structures were confirmed by X-ray diffraction, H-1, C-13 and P-31 NMR. These CyDEPMPOs nitrones showed variable lipophilicities and LD50 values on murine fibroblasts compatible with a safe use in biological spin trapping. All CyDEPMPOs formed persistent spin adducts with a series of free radicals, including superoxide and hydroxyl (i.e., CyDEPMPOs-OH) and the in vitro half-life times of these two latter were at least as extended as those of parent DEPMPO. Using four methods of CyDEPMPOs-OH formation, the cis-CyDEPMPOs-OH percentage was found significantly varied with substitution on the P-containing ring and, more interestingly, with the generating system. (C) 2011 Elsevier Ltd. All rights reserved.
• Novel Sterically Crowded and Conformationally Constrained α-Aminophosphonates with a Near-Neutral pKa as Highly Accurate 31P NMR pH Probes. Application to Subtle pH Gradients Determination in Dictyostelium discoideum Cells
  作者：Caroline Delehedde、Marcel Culcasi、Emilie Ricquebourg、Mathieu Cassien、Didier Siri、Bruno Blaive、Sylvia Pietri、Sophie Thétiot-Laurent

  DOI：10.3390/molecules27144506

  日期：——

  overlapping those of phosphorus metabolites, and spectroscopic sensitivities (i.e., chemical shifts variation Δδab between the acidic and basic forms) ranging from 9.2–10.7 ppm, being fourfold larger than conventional endogenous markers such as inorganic phosphate. X-ray crystallographic studies combined with predictive empirical relationships and ab initio calculations addressed the inductive and

  为了发现新的31 P NMR 标记物用于探测生物环境中的细微 pH 变化（<0.2 pH 单位），合成了 15 种新的构象受限或空间位阻的 α-氨基膦酸盐，它们源自二乙基（2-甲基吡咯烷-2-基）膦酸盐，并测试了它们的 pH 值报告和体外细胞毒性。所有化合物均显示出接近中性的 p K a s（范围为 6.28–6.97）、与磷代谢物不重叠的化学位移和光谱灵敏度（即化学位移变化 Δ δ ab介于酸性和碱性形式之间）范围为 9.2-10.7 ppm，比传统的内源性标记物（如无机磷酸盐）大四倍。X 射线晶体学研究与预测性经验关系和从头计算相结合，解决了与质子化胺功能相关的取代基的诱导和立体化学效应。在 p K a s 与二维结构和磷的金字塔化之间建立了令人满意的相关性，表明磷周围的空间拥挤对于调节 Δ δ ab至关重要。最后，命中31 P NMR pH 探针1b带有未取代的 1,3,2-二氧杂磷环烷环，它具有中等亲脂性，对