膦酸,(3,4-二氢-2,2-二甲基-1-羟基-2H-吡咯-5-基)-,二乙基酯 | 167772-86-3

• 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
• 中文名称: 膦酸,(3,4-二氢-2,2-二甲基-1-羟基-2H-吡咯-5-基)-,二乙基酯
• 英文名称: (5,5-Dimethyl-1-oxy-4,5-dihydro-3H-pyrrol-2-yl)-phosphonic acid diethyl ester
• 英文别名: 5-Diethoxyphosphoryl-2,2-dimethyl-1-oxido-3,4-dihydropyrrol-1-ium
• CAS: 167772-86-3
• 化学式: C₁₀H₂₀NO₄P
• 分子量: 249.247
• InChiKey: SIGTYJLJYPKXFT-UHFFFAOYSA-N

物化性质

• 沸点：
  322.9±25.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  膦酸,(3,4-二氢-2,2-二甲基-1-羟基-2H-吡咯-5-基)-,二乙基酯 在 双氧水 作用下， 生成
  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
• 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 为溶剂， 反应 3.92h， 生成 膦酸,(3,4-二氢-2,2-二甲基-1-羟基-2H-吡咯-5-基)-,二乙基酯
  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
• Combined Ring Inversion and Side Group Rotation in Geminal Diphosphoryl Substituted Pyrrolidinoxyl Radicals:  ESR Analysis of Chemical Exchange between Four Nonequivalent Sites
  作者：Antal Rockenbauer、Anne Mercier、François Le Moigne、Gilles Olive、Paul Tordo

  DOI：10.1021/jp970298o

  日期：1997.10.1

  The ESR spectra of three diphosphorylated pyrrolidinoxyl radicals have been studied over a large temperature range. While for the trans 2,5-disubstituted compound 1 no line width alternation was found, for the 2,2-disubstituted compounds 2 and 3, dramatic changes in the spectra were observed as a function of the temperature. These changes were explained by a four-site chemical exchange model including both ring inversion and hindered rotation around the carbon-phosphorus bonds. For radical 3, the presence of additional 5,5-dimethyl substitution can completely block rotations around carbon-phosphorus bonds for certain ring geometries, while for other ring conformations chemical exchange still occurs through combined inversion-rotation processes. An effective two-site model composed of nonequivalent sites and a superposition model composed of a pair of exchanging conformers and a pair of nonexchanging conformers were used to simulate spectrum variations. A satisfactory fit was obtained over the entire temperature range investigated. From the temperature dependence of the exchange frequencies the potential barriers for ring inversion (27 kJ/mol), for combined inversion-rotation (11 kJ/mol), and for rotation around the carbon-phosphorus bonds (14 kJ/mol) were estimated.
• 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.