ethyl 2-((tert-butyl(1-(diethoxyphosphoryl)-2,2-dimethylpropyl)amino)oxy)-2-methylpropanoate | 1034132-98-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: ethyl 2-((tert-butyl(1-(diethoxyphosphoryl)-2,2-dimethylpropyl)amino)oxy)-2-methylpropanoate
• 英文别名: ethyl 2-methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]propinoate；ethyl 2-methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]propionate；Ethyl 2-[tert-butyl-[1-[diethoxy(oxido)phosphaniumyl]-2,2-dimethylpropyl]amino]oxy-2-methylpropanoate
• CAS: 1034132-98-3
• 化学式: C₁₉H₄₀NO₆P
• 分子量: 409.503
• InChiKey: ISOYNAMDTJZIDE-UHFFFAOYSA-N

物化性质

• 沸点：
  444.3±55.0 °C(Predicted)
• 密度：
  1.032±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  27
• 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：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ethyl 2-((tert-butyl(1-(diethoxyphosphoryl)-2,2-dimethylpropyl)amino)oxy)-2-methylpropanoate 以 叔丁醇 为溶剂， 反应 48.0h， 生成 diethyl (1-(tert-butyl((ethoxycarbonyl)oxy)amino)-2,2-dimethylpropyl)phosphonate
  参考文献：
  名称：

  Direct functionalization of labile alkoxyamines

  摘要：

  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.

  DOI：

  10.1016/j.tetlet.2012.06.049
• 作为产物：
  描述：

  2-溴-2-甲基丙酸乙酯 、 N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] 在 五甲基二乙烯三胺 、 铜 作用下， 以 二甲基亚砜 为溶剂， 生成 ethyl 2-((tert-butyl(1-(diethoxyphosphoryl)-2,2-dimethylpropyl)amino)oxy)-2-methylpropanoate
  参考文献：
  名称：

  Cu（0）介导的活性自由基聚合的起始步骤中的歧化与歧化

  摘要：

  我们目前对铜（0）介导的原子转移自由基聚合（也称为SET-LRP或SARA ATRP）中起始步骤的研究，其中存在一个氮氧自由基，N-叔丁基-N- [1-二乙基膦酰基-（2,2-二甲基丙基）]氮氧化物（SG1）用于捕获衍生自2-溴异丁酸乙酯（EBiB），铜金属和五甲基二亚乙基三胺（PMDETA）配体的自由基。建立了一个动力学模型，该模型将EBiB的转化率与铜金属的活化速率常数（k a0）和Cu 0和Cu II的比例化（k comp）联系起来。）。这样就可以在几种溶剂中测定这些参数，包括二甲基亚砜（DMSO），二甲基甲酰胺（DMF），乙醇（EtOH）和乙腈（MeCN），其中观察到明显的歧化水平，从而导致反应自动加速。根据先前公布的实验数据，对铜介导的聚合动力学的类似处理可预测引发剂浓度和铜表面积的1/2阶依赖性。

  DOI：

  10.1021/ma301034t

文献信息

• Synthesis of Highly Labile SG1-Based Alkoxyamines under Photochemical Conditions
  作者：Yohann Guillaneuf、Jean-Luc Couturier、Didier Gigmes、Sylvain R. A. Marque、Paul Tordo、Denis Bertin

  DOI：10.1021/jo800422a

  日期：2008.6.1

  Highly labile SG1-based alkoxyamines were synthesized using the photodecomposition of both azo compounds and dithiocarbamates. The former method was a straightforward procedure to obtain the alkoxyamines, but a high [azo]/[nitroxide] ratio is needed. The latter method required only a stoichiometric amount of dithiocarbamate and allowed the recovery of the disulfide after irradiation. This enabled combination of the two methods in a process where only 0.75 equiv of azo compound is needed and where sulfurous compounds acted only as intermediates.
• 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