methyl 2-methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]propionate

• 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: methyl 2-methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]propionate
• 英文别名: Methyl 2-[tert-butyl-(1-diethoxyphosphoryl-2,2-dimethylpropyl)amino]oxy-2-methylpropanoate；methyl 2-[tert-butyl-(1-diethoxyphosphoryl-2,2-dimethylpropyl)amino]oxy-2-methylpropanoate
• 化学式: C₁₈H₃₈NO₆P
• 分子量: 395.477
• InChiKey: UYMAIJRQYJNTKY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  26
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.94
• 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：

  methyl 2-methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]propionate 生成 异丁酸甲酯 、 二乙基亚磷酸氢酯
  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-溴代异丁酸甲酯 、 N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl 在 copper bromide 、 五甲基二乙烯三胺 、 铜 作用下， 以 苯 为溶剂， 反应 0.5h， 以80%的产率得到methyl 2-methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]propionate
  参考文献：
  名称：

  烷氧基胺 C-ON 键均裂：立体电子效应

  摘要：

  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) 反应的重要调节剂。由于聚合时间随着聚合物链和硝酰基部分之间的 C-ON 键均裂的速率常数的增加而减少，因此影响裂解速率常数的因素非常重要。因此，有趣的是检查在基于 TEMPO 的烷氧基胺系列中观察到的甲基效应（对于添加到 C-ON 键的碳原子上的每个甲基，+17 kJ/mol）是否也在 SG1 [N-tert -丁基-N-(1-二乙氧基磷酰基-2,2-二甲基丙基)氨氧基]系列。此外，我们扩展了先前提出的增量取代基尺度，并证实了先前工作中开发的多参数分析的多功能性。几种 SG1-CHMeCOOR 烷氧基胺的 X 射线和自然键轨道 (NBO) 分析表明，(RR/SS) 和 (RS/SR) 非对映异构体之间的反应性差异是由 nσ 孤对之间的 nσσ* 相互作用引起的酯键的氧原子和裂解的 O-C 键的 σ* 轨道。此外，对离开烷基自由基对

  DOI：

  10.1002/ejoc.200500725

文献信息

• Process for the preparation of sterically hindered nitroxyl ethers
  申请人：Schöning Kai-Uwe

  公开号：US20100249401A1

  公开（公告）日：2010-09-30

  The present invention relates to a novel process for the preparation of a sterically hindered nitroxyl ether from the corresponding sterically hindered nitroxyl radical by reacting it with a carbonyl compound and a hydroperoxide. The compounds prepared by this process are effective stabilizers for polymers against harmful effects of light, oxygen and/or heat, as flame-retardants for polymers and as polymerization regulators.

  本发明涉及一种从相应的立体位阻的亚硝基自由基通过与羰基化合物和过氧化氢反应制备立体位阻的亚硝基醚的新工艺。通过该工艺制备的化合物是聚合物的有效稳定剂，可抵抗光、氧和/或热的有害影响，作为聚合物的阻燃剂和聚合物化合物的调节剂。
• 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。
• 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.
• Direct functionalization of labile alkoxyamines
  作者：Paul Brémond、Kuanysh Kabytaev、Sylvain R.A. Marque

  DOI：10.1016/j.tetlet.2012.06.049

  日期：2012.8

  Direct esterification of a labile alkoxyamine (RRNOR3)-R-1-N-2, which was previously reported as unsuccessful, is achieved by a Mitsunobu reaction or a nucleophilic substitution. Ester derivatives are obtained under smooth conditions and easily purified. Macrocyclization attempts on ester derivatives were successful for five-membered ring lactones and unsuccessful for 13-membered ring lactones. Moreover, the success of the cyclization was dramatically dependent on the quality of the solution degassing. Poor degassing led to unexpected carbonate alkoxyamine. (C) 2012 Elsevier Ltd. All rights reserved.
• ALCOXYAMINES ISSUES DE NITROXYDES BETA-PHOSPHORES
  申请人：Arkema France

  公开号：EP1527079B1

  公开（公告）日：2006-12-20