2,2,5,5-tetramethyl-3-(1-phenylethoxy)-4-diethylphosphono-3-azahexane | 224575-62-6

• 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: 2,2,5,5-tetramethyl-3-(1-phenylethoxy)-4-diethylphosphono-3-azahexane
• 英文别名: phosphonic acid [1-[(1,1-dimethylethyl)(1-phenylethoxy)amino]-2,2-dimethylpropyl]-diethyl ester；N-tert-butyl-N-1-diethylphosphono-2,2-dimethylpropyl-O-1-phenylethylhydroxyl-amine；N-tert-butyl-1-diethoxyphosphoryl-2,2-dimethyl-N-(1-phenylethoxy)propan-1-amine
• CAS: 224575-62-6
• 化学式: C₂₁H₃₈NO₄P
• 分子量: 399.511
• InChiKey: WFUISZSLILUYMT-UHFFFAOYSA-N

物化性质

• 熔点：
  10-15 °C
• 沸点：
  456.4±55.0 °C(Predicted)
• 密度：
  1.028±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  27
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  2,2,5,5-tetramethyl-3-(1-phenylethoxy)-4-diethylphosphono-3-azahexane 以 various solvent(s) 为溶剂， 生成 1-phenylethyl radical 、 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：

  (1-溴乙基)苯 在 lead dioxide 、 肼 作用下， 反应 1.08h， 生成 2,2,5,5-tetramethyl-3-(1-phenylethoxy)-4-diethylphosphono-3-azahexane
  参考文献：
  名称：

  用于“活性”自由基聚合的通用烷氧基胺的开发

  摘要：

  对新型烷氧基胺的研究表明，硝基氧在介导各种乙烯基单体的“活性”或受控聚合方面发挥着关键作用。调查各种不同的烷氧基胺结构导致基于 2,2,5-trimethyl-4-phenyl-3-azahex-3-oxy, 1, 骨架的 α-氢化衍生物能够控制苯乙烯、丙烯酸酯的聚合、丙烯酰胺和丙烯腈基单体。对于每个单体组，分子量可以控制在 1000 到 200 000 amu 之间，多分散性通常为 1.05-1.15。基于上述单体的组合的嵌段和无规共聚物也可以用类似的控制来制备。与 2,2,6,6-四甲基哌啶氧基 (TEMPO) 相比，这些新系统代表了可在受控条件下聚合的单体范围的显着增加，并克服了与氮氧化合物介导的“活性”自由基程序相关的许多限制。单体选择和功能...

  DOI：

  10.1021/ja984013c

文献信息

• Method for prepararing alkoxyamines from nitroxides
  申请人：——

  公开号：US20030050507A1

  公开（公告）日：2003-03-13

  The invention concerns a method for preparing alkoxyamines in a biphasic medium. Said method consists in mixing an ionic liquid, an organic solvent, a metal salt, a metal ligand, a halogeno-carbonaceous ZX compound and a nitroxide, maintaining the reaction medium under agitation at a temperature between 20° C. and 90° C., until the nitroxide is eliminated, decanting, recuperating the organic phase, optionally washing it with water and then in isolating the alkoxyamine by evaporating the organic solvent under reduced pressure.

  该发明涉及一种在两相介质中制备烷氧胺的方法。该方法包括混合离子液体、有机溶剂、金属盐、金属配体、卤代碳氢ZX化合物和亚硝基，在20°C至90°C的温度下将反应介质保持在搅拌状态，直到亚硝基被消除，然后沉淀，回收有机相，可选地用水洗涤，然后通过在减压下蒸发有机溶剂来分离烷氧胺。
• [EN] BLACK PIGMENT DISPERSION<br/>[FR] DISPERSION DE PIGMENT NOIR
  申请人：BASF SE

  公开号：WO2010081756A1

  公开（公告）日：2010-07-22

  Described is a pigment dispersion which is useful for electrophoretic displays comprising α) a bis-oxodihydro-indolylene-benzodifuranone colourant of the Formula (I) wherein the substituents are defined as in claim 1, β) a specific polymeric dispersant, and γ) a solvent which is suitable for dispersions used in electrophoretic displays. Also described are novel colourants and dispersants.

  描述了一种用于电泳显示的颜料分散剂，包括α）公式（I）中的双氧二氢吲哚基苯并二呋喃酮颜料，其中取代基的定义如权利要求1所述，β）特定的聚合物分散剂，和γ）适用于电泳显示中使用的分散剂的溶剂。还描述了新颖的颜料和分散剂。
• Stereochemical Studies of Chiral Acyclic Nitroxides Coupling with a Prochiral Radical
  作者：Rebecca Braslau、Vladimir Chaplinski、Aaron Nilsen、Navamoney Arulsamy

  DOI：10.1081/scc-120039497

  日期：2004.1.1

  Abstract A series of acyclic chiral nitroxides bearing a hydrogen atom on the carbon adjacent to the nitroxide nitrogen was investigated for stereoselectivity in a coupling reaction with the prochiral radical 1‐phenethyl. In one case, an x‐ray structure of the major diastereomer was obtained, which corroborates a model for predicting the stereoselectivity.

  摘要 研究了一系列在与氮氧氮相邻的碳上带有一个氢原子的无环手性氮氧化合物在与前手性基团 1-苯乙基的偶联反应中的立体选择性。在一个案例中，获得了主要非对映异构体的 X 射线结构，这证实了预测立体选择性的模型。
• 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。
• Controlled Polymerization of Functional Monomers and Synthesis of Block Copolymers Using a β-Phosphonylated Nitroxide
  作者：T. Diaz、A. Fischer、A. Jonquières、A. Brembilla、P. Lochon

  DOI：10.1021/ma0260086

  日期：2003.4.1

  4-Vinylpyridine (4VP) and N,N-dimethylacrylamide (DMAA) were polymerized in a controlled manner using a beta-phosphonylated nitroxide (N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) nitroxide, commonly designated as DEPN) as a control agent. Compared to the results that had previously been reported for the nitroxide-mediated radical polymerization (NMRP) with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), the polymerization of 4VP was much faster and very well controlled up to higher monomer conversions. Unlike 4VP, the controlled radical polymerization of DMAA using different types of nitroxides had so far remained limited to a very low conversion range (typically inferior to 10%). The use of DEPN gave rise to a very significant improvement of the NMRP of DMAA by providing a good reaction control up to high conversion (approximately 60%). For the first time, the ability of DEPN to control the homopolymerization of DMAA even at high conversion allowed the synthesis of poly(DMAA-b-4VP) block copolymers with a hydrophilic poly(DMAA) block which was longer than the poly(4VP) block. This particular feature should fairly improve the hydrosolubility of the derived amphiphilic cationic polymers, which can be obtained by simple quaternization of the former block copolymers, and extend the scope of their applications.