2-diethoxyphosphoryl-2,5,5-trimethylpyrrolidine-N-oxyl radical | 130208-30-9

• 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-diethoxyphosphoryl-2,5,5-trimethylpyrrolidine-N-oxyl radical
• 英文别名: 2-diethoxyphosphoryl-2,5,5-trimethyl(pyrrolidin-1-yloxyl)；2-diethoxyphosphoryl-2,5,5-trimethylpyrrolidine-1-oxyl；TMPPO
• CAS: 130208-30-9
• 化学式: C₁₁H₂₃NO₄P
• 分子量: 264.282
• InChiKey: MGOXVYGWEQGJBC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-diethoxyphosphoryl-2,5,5-trimethylpyrrolidine-N-oxyl radical 在 1,4,7-triazaheptane-1,1,7,7-tetraacetic acid 、 photopedused flavine 作用下， 以 various solvent(s) 为溶剂， 生成 (1-Hydroxy-2,5,5-trimethyl-pyrrolidin-2-yl)-phosphonic acid diethyl ester
  参考文献：
  名称：

  Mathieu, Corinne; Tuccio, Beatrice; Lauricella, Robert, Journal of the Chemical Society. Perkin Transactions 2 (2001), 1997, # 12, p. 2501 - 2505

  摘要：

  DOI：
• 作为产物：
  描述：

  5,5-二甲基-1-吡咯啉-N-氧化物 在 ammonium hydroxide 、 copper diacetate 、 air 、 lithium diisopropyl amide 作用下， 以 乙醇 、 二氯甲烷 、 苯 为溶剂， 反应 3.92h， 生成 2-diethoxyphosphoryl-2,5,5-trimethylpyrrolidine-N-oxyl radical
  参考文献：
  名称：

  Identification of Reactive Free Radicals with a New 31P-Labeled DMPO Spin Trap

  摘要：

  The P-31 atom (I = 1/2) can provide additional useful EPR information when it is introduced into the 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin trap. 2-(Diethylphosphono)-5,5-dimethyl-1-pyrroline N-oxide (DEP-DMPO) has been synthesized by addition of diethylphosphono anion to DMPO followed by oxidation with copper acetate/air in 95% ethanol. DEP-DMPO is a liquid at room temperature and soluble in both aqueous and organic solutions. A variety of spin trapping experiments have been explored. The main feature of the EPR spectra of DEP-DMPO spin adducts is the relatively large doublet of triplets. The P-31 hyperfine splitting constant (P-31-hfsc or a(p)) in these examples is always larger than the N-hfsc. For oxygen-centered radical adducts, e.g., from HOO., HO., n-BuO(.), i-BuO(.), and isoamylO(.), a(P)'s are 32.3-34.5 G whereas a(N)'s are 13.4-14.1 G in water. For acyl adducts, such as CH3(CH2)(4)C(O)(.), C2H5C(O)(.), CH3C(O)(.), and (CO2)-C-., a(P)'s are 38.6-39.2 G whereas a(N)'s are 14.3-14.8 G in water; a(P)'s for alkyl and hydroxyalkyl radical adducts are between 48.1 and 54.6 G in water; for the phenyl adduct the value is exceptionally small, a(p) = 31.5 G. Most of the adducts are very persistent in aqueous solutions, e.g., t(1/2) = 3.0 h for HO. adduct, 31.5 h for i-amylO(.) adduct, and 52.4 h for CH3C(O)(.) adduct in water. However, the hydroperoxyl and tert-butylperoxyl adducts decay rapidly: t(1/2) = 3.6 s in water and t(1/2) = 4.3 s in isooctane, respectively.

  DOI：

  10.1021/jo00122a022

文献信息

• New, stable β-phosphorus-labelled pyrrolidine nitroxides from nitrones for magnetometry: an ESR investigation
  作者：D. Lawrence Haire、Edward G. Janzen、Guoman Chen、Valerie J. Robinson、Ivan Hrvoic

  DOI：10.1002/(sici)1097-458x(199904)37:4<251::aid-mrc406>3.0.co;2-m

  日期：1999.4

  nitrogen hyperfine splitting, the present special nitroxide displays little change in the nitroxide nitrogen splitting (Δa N≈0.03 mT). A very robust variation in the β‐31P hyperfine splitting (Δa N≈0.35 mT), however, is observed. Hence it may be a much more sensitive pH probe molecule than Keana et al .'s. It is proposed that this ESR variation for the present nitroxide is due to conformational changes

  本研究致力于设计和合成用于动态核极化 (DNP) 磁力计的新型原型氮氧化物。具体来说，合成了八种 β-磷酸化吡咯烷氮氧化物。它们的大（约 5.0 mT）β-31 P 超精细分裂使它们成为磁力测量应用的理想选择。其中七个自由基是 2-二烷基亚磷酰基-2,5,5-三烷基-或 2-二芳基亚磷酰基-2,5,5-三烷基吡咯烷氮氧化物。研究了结构和溶剂对这些氮氧化物的 ESR 光谱的影响。亚磷酸基团的水解产生显着的第八个氮氧化合物。它表现出极其依赖 pH 值的 ESR 谱。已知其他氮氧化物（例如 β-氨基）显示出依赖于 pH 值的 ESR 光谱（ΔaN≈0.15 mT），这些已由 Keana 等人提出。作为新型、灵敏的 pH 指示剂。虽然它们通过氮氧氮超精细分裂的变化起作用，但目前的特殊氮氧化合物在氮氧氮分裂中几乎没有变化（Δa N≈0.03 mT）。然而，观察到 β-31P 超精细分裂（Δa N≈0
• β-Phosphorylated five membered ring nitroxides, a new class of stable nitroxides. 1. Synthesis by Reaction. of dialkylphosphites with 1-pyrroline-n-oxides.
  作者：Anne Mercier、Yves Berchadsky、Badrudin、Pietri Sylvia、Paul Tordo

  DOI：10.1016/s0040-4039(00)71253-6

  日期：1991.5

  Dialkylphosphites add to 2,5,5-trialkyl-1-pyrroline-N-oxides to give, after oxidation with copper(II)acetate, the corresponding β-phosphorylated nitroxides, which are stable in many organic solvents.

  亚磷酸二烷基酯加到2,5,5-三烷基-1-吡咯啉-N-氧化物中，在用乙酸铜（II）氧化后，生成相应的β-磷酸化的氮氧化物，在许多有机溶剂中稳定。
• β-Phosphorylated cyclic nitroxides. 2. Synthesis of pyrrolidin- and piperidin-2-yl phosphonates and the corresponding stable nitroxides.
  作者：Francois Le Moigne、Anne Mercier、Paul Tordo

  DOI：10.1016/s0040-4039(00)79391-9

  日期：1991.7

  Alkenyl α-aminophosphonates are cyclized by intramolecular aminomercuration to give pyrrolidin- and piperidin-2-yl phosphonates which lead, after oxidation with m-CPBA, to the corresponding stable β-phosphorylated nitroxides.

  烯基α-氨基膦酸酯通过分子内氨基汞化而环化，得到吡咯烷基-和哌啶-2-基膦酸酯，其在用m-CPBA氧化后可导致相应的稳定的β-磷酸化的氮氧化物。
• Identification of Reactive Free Radicals with a New 31P-Labeled DMPO Spin Trap
  作者：Edward G. Janzen、Yong-Kang Zhang

  DOI：10.1021/jo00122a022

  日期：1995.9

  The P-31 atom (I = 1/2) can provide additional useful EPR information when it is introduced into the 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin trap. 2-(Diethylphosphono)-5,5-dimethyl-1-pyrroline N-oxide (DEP-DMPO) has been synthesized by addition of diethylphosphono anion to DMPO followed by oxidation with copper acetate/air in 95% ethanol. DEP-DMPO is a liquid at room temperature and soluble in both aqueous and organic solutions. A variety of spin trapping experiments have been explored. The main feature of the EPR spectra of DEP-DMPO spin adducts is the relatively large doublet of triplets. The P-31 hyperfine splitting constant (P-31-hfsc or a(p)) in these examples is always larger than the N-hfsc. For oxygen-centered radical adducts, e.g., from HOO., HO., n-BuO(.), i-BuO(.), and isoamylO(.), a(P)'s are 32.3-34.5 G whereas a(N)'s are 13.4-14.1 G in water. For acyl adducts, such as CH3(CH2)(4)C(O)(.), C2H5C(O)(.), CH3C(O)(.), and (CO2)-C-., a(P)'s are 38.6-39.2 G whereas a(N)'s are 14.3-14.8 G in water; a(P)'s for alkyl and hydroxyalkyl radical adducts are between 48.1 and 54.6 G in water; for the phenyl adduct the value is exceptionally small, a(p) = 31.5 G. Most of the adducts are very persistent in aqueous solutions, e.g., t(1/2) = 3.0 h for HO. adduct, 31.5 h for i-amylO(.) adduct, and 52.4 h for CH3C(O)(.) adduct in water. However, the hydroperoxyl and tert-butylperoxyl adducts decay rapidly: t(1/2) = 3.6 s in water and t(1/2) = 4.3 s in isooctane, respectively.
• Mathieu, Corinne; Tuccio, Beatrice; Lauricella, Robert, Journal of the Chemical Society. Perkin Transactions 2 (2001), 1997, # 12, p. 2501 - 2505
  作者：Mathieu, Corinne、Tuccio, Beatrice、Lauricella, Robert、Mercier, Anne、Tordo, Paul

  DOI：——

  日期：——