2-{N-tert-butyl-N-[1-(diethyl-phosphoryl)-2,2-dimethyl-propyl]-aminooxy}-2-methyl-propionic acid tert-butyl ester

• 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-{N-tert-butyl-N-[1-(diethyl-phosphoryl)-2,2-dimethyl-propyl]-aminooxy}-2-methyl-propionic acid tert-butyl ester
• 英文别名: Tert-butyl 2-[tert-butyl-(1-diethoxyphosphoryl-2,2-dimethylpropyl)amino]oxy-2-methylpropanoate；tert-butyl 2-[tert-butyl-(1-diethoxyphosphoryl-2,2-dimethylpropyl)amino]oxy-2-methylpropanoate
• 化学式: C₂₁H₄₄NO₆P
• 分子量: 437.557
• InChiKey: SZABWPWVVVWTHN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  29
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  74.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-{N-tert-butyl-N-[1-(diethyl-phosphoryl)-2,2-dimethyl-propyl]-aminooxy}-2-methyl-propionic acid tert-butyl ester 生成 甲基丙烯酸叔丁酯 、 二乙基亚磷酸氢酯 、 Tert-butyl [tert-butyl-[1-[diethoxy(oxido)phosphaniumyl]-2,2-dimethylpropyl]amino] carbonate 、 N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl
  参考文献：
  名称：

  H-transfer reaction during decomposition ofN-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1)-based alkoxyamines

  摘要：

  AbstractThermal decomposition of four tertiary N‐(2‐methylpropyl)‐N‐(1‐diethylphosphono‐2,2‐dimethylpropyl)‐N‐oxyl (SG1)‐based alkoxyamines (SG1‐C(Me)2‐C(O)‐OR, R = Me, tBu, Et, H) has been studied at different experimental conditions using 1H and 31P NMR spectroscopies. This experiment represents the initiating step of methyl methacrylate polymerization. It has been shown that H‐transfer reaction occurs during the decomposition of three alkoxyamines in highly degassed solution, whereas no products of H‐transfer are detected during decomposition of SG1‐MAMA alkoxyamine. The value of the rate constant of H‐transfer for alkoxyamines 1 (SG1‐C(Me)2‐C(O)‐OMe) and 2 (SG1‐C(Me)2‐C(O)‐OtBu) has been estimated as 1.7 × 103 M−1s−1. The high influence of oxygen on decomposition mechanism is found. In particular, in poorly degassed solutions, nearly quantitative formation of oxidation product has been observed, whereas at residual pressure of 10−5 mbar, the main products originate from H‐atom transfer reaction. The acidity of the reaction medium affects the decomposition mechanism suppressing the H‐atom transfer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

  DOI：

  10.1002/pola.26500
• 作为产物：
  描述：

  2-溴代异丁酸叔丁酯 、 N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl 在 五甲基二乙烯三胺 、 铜 、 copper(I) bromide 作用下， 以 丙酮 为溶剂， 以70%的产率得到2-{N-tert-butyl-N-[1-(diethyl-phosphoryl)-2,2-dimethyl-propyl]-aminooxy}-2-methyl-propionic acid tert-butyl ester
  参考文献：
  名称：

  在非对映体烷氧基胺的裂解和重整时，非对映体过量。

  摘要：

  通过（1）H和（1）研究了几种基于TEMPO和DEPN（N-（2-甲基丙-2-基）-N-（1-二乙基膦酰基-2,2-二甲基丙基）-氨基二甲苯基）的烷氧基​​胺的热反应。 31）P NMR光谱法，旨在区分非对映选择性均解和偶联对总平衡非对映异构体分布的贡献。基于TEMPO的化合物未显示出非对映异构体过量，而基于DEPN的化合物在均质和偶联后均显示出适度的过量。DEPN-（丙酸酯样）加合物的均相非对映异构偏好不取决于酯基，它主要受β取代基大小的影响。非对映选择性偶联对总重组速率常数k（c）敏感，并且非对映选择性随k（c）的降低而增加。

  DOI：

  10.1039/b313990e

文献信息

• Alkoxyamines originating from $g(b)-phoshorylated nitroxides and use thereof in radical polymerisation
  申请人：Couturier Luc Jean

  公开号：US20060142511A1

  公开（公告）日：2006-06-29

  A subject-matter of the invention is alkoxyamines resulting from β-phosphorated nitroxides corresponding to the formula: These compounds can be used as initiators for the (co)polymerizations of at least one monomer which can be polymerized by the radical route.

  本发明的一个主题是由式中β-磷化亚硝基产生的烷氧基胺： 这些化合物可用作至少一种可通过自由基途径聚合的单体的（共）聚合引发剂。
• US7772340B2
  申请人：——

  公开号：US7772340B2

  公开（公告）日：2010-08-10
• Diastereomeric excess upon cleavage and reformation of diastereomeric alkoxyamines
  作者：Gennady Ananchenko、Sylvain Marque、Didier Gigmes、Denis Bertin、Paul Tordo

  DOI：10.1039/b313990e

  日期：——

  DEPN (N-(2-methylpropan-2-yl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-aminoxyl) based alkoxyamines were studied by means of (1)H and (31)P NMR spectroscopy aiming to distinguish the contributions of diastereoselective homolysis and coupling to the total equilibrium diastereomeric distribution. The TEMPO-based compounds reveal no diastereomeric excess while DEPN based compounds show a moderate excess

  通过（1）H和（1）研究了几种基于TEMPO和DEPN（N-（2-甲基丙-2-基）-N-（1-二乙基膦酰基-2,2-二甲基丙基）-氨基二甲苯基）的烷氧基​​胺的热反应。 31）P NMR光谱法，旨在区分非对映选择性均解和偶联对总平衡非对映异构体分布的贡献。基于TEMPO的化合物未显示出非对映异构体过量，而基于DEPN的化合物在均质和偶联后均显示出适度的过量。DEPN-（丙酸酯样）加合物的均相非对映异构偏好不取决于酯基，它主要受β取代基大小的影响。非对映选择性偶联对总重组速率常数k（c）敏感，并且非对映选择性随k（c）的降低而增加。
• H-transfer reaction during decomposition of<i>N</i>-(2-methylpropyl)-<i>N</i>-(1-diethylphosphono-2,2-dimethylpropyl)-<i>N</i>-oxyl (SG1)-based alkoxyamines
  作者：Mariya Edeleva、Sylvain R. A. Marque、Kuanish Kabytaev、Yohann Guillaneuf、Didier Gigmes、Elena Bagryanskaya

  DOI：10.1002/pola.26500

  日期：2013.3.15

  AbstractThermal decomposition of four tertiary N‐(2‐methylpropyl)‐N‐(1‐diethylphosphono‐2,2‐dimethylpropyl)‐N‐oxyl (SG1)‐based alkoxyamines (SG1‐C(Me)2‐C(O)‐OR, R = Me, tBu, Et, H) has been studied at different experimental conditions using 1H and 31P NMR spectroscopies. This experiment represents the initiating step of methyl methacrylate polymerization. It has been shown that H‐transfer reaction occurs during the decomposition of three alkoxyamines in highly degassed solution, whereas no products of H‐transfer are detected during decomposition of SG1‐MAMA alkoxyamine. The value of the rate constant of H‐transfer for alkoxyamines 1 (SG1‐C(Me)2‐C(O)‐OMe) and 2 (SG1‐C(Me)2‐C(O)‐OtBu) has been estimated as 1.7 × 103 M−1s−1. The high influence of oxygen on decomposition mechanism is found. In particular, in poorly degassed solutions, nearly quantitative formation of oxidation product has been observed, whereas at residual pressure of 10−5 mbar, the main products originate from H‐atom transfer reaction. The acidity of the reaction medium affects the decomposition mechanism suppressing the H‐atom transfer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013