N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)-O-(benzyl)hydroxylamine | 224575-61-5

• 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: N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)-O-(benzyl)hydroxylamine
• 英文别名: N-tert-butyl-N-1-diethylphosphono-2,2-dimethylpropyl-O-benzyl-hydroxylamine；N-tert-butyl-1-diethoxyphosphoryl-2,2-dimethyl-N-phenylmethoxypropan-1-amine
• CAS: 224575-61-5
• 化学式: C₂₀H₃₆NO₄P
• 分子量: 385.484
• InChiKey: FGKSGPUOJMKTJJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  26
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  48
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)-O-(benzyl)hydroxylamine 以 various solvent(s) 为溶剂， 生成 癸酸苄酯 、 N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl
  参考文献：
  名称：

  Entropy Control of the Cross-Reaction between Carbon-Centered and Nitroxide Radicals

  摘要：

  Absolute rate constants for the cross-coupling reaction of several carbon-centered radicals with various nitroxides and their temperature dependence have been determined in liquids by kinetic absorption spectroscopy. The rate constants range from <2 x 10(5) M-1 s(-1) to 2.3 x 10(9) M-1 s(-1) and depend strongly on the structure of the nitroxide and the carbon-centered radical. Grossly, they decrease with increasing rate constant of the cleavage of the corresponding alkoxyamine. In many cases, the temperature dependence shows a non-Arrhenius behavior. A model assuming a short-lived intermediate that is hindered to form the coupling product by an unfavorable activation entropy leads to a satisfactory analytic description. However, the behavior is more likely due to a barrierless single-step reaction with a low exothermicity where the free energy of activation is dominated by a large negative entropy term.

  DOI：

  10.1021/ja0036460
• 作为产物：
  描述：

  癸酸苄酯 、 N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl 以 various solvent(s) 为溶剂， 生成 N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)-O-(benzyl)hydroxylamine
  参考文献：
  名称：

  Entropy Control of the Cross-Reaction between Carbon-Centered and Nitroxide Radicals

  摘要：

  Absolute rate constants for the cross-coupling reaction of several carbon-centered radicals with various nitroxides and their temperature dependence have been determined in liquids by kinetic absorption spectroscopy. The rate constants range from <2 x 10(5) M-1 s(-1) to 2.3 x 10(9) M-1 s(-1) and depend strongly on the structure of the nitroxide and the carbon-centered radical. Grossly, they decrease with increasing rate constant of the cleavage of the corresponding alkoxyamine. In many cases, the temperature dependence shows a non-Arrhenius behavior. A model assuming a short-lived intermediate that is hindered to form the coupling product by an unfavorable activation entropy leads to a satisfactory analytic description. However, the behavior is more likely due to a barrierless single-step reaction with a low exothermicity where the free energy of activation is dominated by a large negative entropy term.

  DOI：

  10.1021/ja0036460

文献信息

• Factors Influencing C−ON Bond Homolysis in Alkoxyamines:  Unexpected Behavior of SG1 (<i>N</i>-(2-methyl-2-propyl)- <i>N</i>-(1-diethylphosphono-2,2-dimethylpropyl)-<i>N</i>-oxyl)-Based Alkoxyamines
  作者：Denis Bertin、Didier Gigmes、Christophe Le Mercier、Sylvain R. A. Marque、Paul Tordo

  DOI：10.1021/jo0495586

  日期：2004.7.1

  Alkoxyamines and persistent nitroxides are important regulators of nitroxide-mediated radical polymerization (NMP). Since the polymerization time decreases with the increasing equilibrium constant K (kd/kc), i.e., the increasing rate constant kd of the homolysis of the C−ON bond between the polymer chain and the nitroxide moiety, the factors influencing the cleavage rate constants are of considerable

  烷氧基胺和持久性氮氧化物是氮氧化物介导的自由基聚合（NMP）的重要调节剂。由于聚合时间随着平衡常数K（k d / k c）的增加而减少，即聚合物链和氮氧化物部分之间C-ON键均化的速率常数k d的增加，因此影响裂解的因素速率常数引起了极大的兴趣。事实证明，基于SG1的烷氧基胺是用于各种单体NMP的最有效的烷氧基胺家族。因此，确定使SG1衍生物比TEMPO（2,2,6,6-四甲基哌啶-N-氧基）衍生物。与我们对TEMPO衍生物观察到的相反，我们观察到E a与BDE（CH）的关系有两个关系，一个关系是非极性释放的烷基自由基（E a（kJ / mol）= -133.0 + 0.72BDE）和另一个用于极性释放的烷基（E a（kJ / mol）= -137.0 + 0.69BDE）。然而，对于两个家族（SG1和TEMPO衍生物），C-ON键均解的速率常数k d与裂解温度T c相关（log（k d（s
• ALCOXYAMINES ISSUES DE NITROXYDE BETA-PHOSPHORES, LEUR UTILISATION EN POLYMERISATION RADICALAIRE
  申请人：Atofina

  公开号：EP1153030B1

  公开（公告）日：2002-09-11
• US6569967B1
  申请人：——

  公开号：US6569967B1

  公开（公告）日：2003-05-27
• Entropy Control of the Cross-Reaction between Carbon-Centered and Nitroxide Radicals
  作者：Jens Sobek、Rainer Martschke、Hanns Fischer

  DOI：10.1021/ja0036460

  日期：2001.3.1

  Absolute rate constants for the cross-coupling reaction of several carbon-centered radicals with various nitroxides and their temperature dependence have been determined in liquids by kinetic absorption spectroscopy. The rate constants range from <2 x 10(5) M-1 s(-1) to 2.3 x 10(9) M-1 s(-1) and depend strongly on the structure of the nitroxide and the carbon-centered radical. Grossly, they decrease with increasing rate constant of the cleavage of the corresponding alkoxyamine. In many cases, the temperature dependence shows a non-Arrhenius behavior. A model assuming a short-lived intermediate that is hindered to form the coupling product by an unfavorable activation entropy leads to a satisfactory analytic description. However, the behavior is more likely due to a barrierless single-step reaction with a low exothermicity where the free energy of activation is dominated by a large negative entropy term.