4-(1-萘甲酰氧基)-2,2,6,6-四甲基哌啶-1-氧自由基 | 95676-89-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 中文名称: 4-(1-萘甲酰氧基)-2,2,6,6-四甲基哌啶-1-氧自由基
• 英文名称: 2,2,6,6-tetramethyl-4-(1-naphthoyloxy)-1-piperidinyloxyl radical
• 英文别名: 4-(1-Naphthoyloxy)-2,2,6,6-tetramethylpiperidine-1-oxyl；4-(1-naphthoate)-2,2,6,6-tetramethylpiperidine-1-oxyl；1-oxy-2,2,6,6-tetramethylpiperidin-4-yl 1-naphthoate；NTEMPO
• CAS: 95676-89-4
• 化学式: C₂₀H₂₄NO₃
• 分子量: 326.415
• InChiKey: KRUFSEDKEYJKKH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  30.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(1-萘甲酰氧基)-2,2,6,6-四甲基哌啶-1-氧自由基 在 palladium on activated charcoal 吡啶 、 氢气 作用下， 以 四氢呋喃 为溶剂， 反应 23.0h， 生成 1-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl 1-naphthoate
  参考文献：
  名称：

  稳定的硝酰基自由基对激发单线态的分子内猝灭

  摘要：

  吸光度和稳态和时间分辨荧光测量被用来检查激发单线态猝灭的一系列氮氧化物荧光团加合物中的氮氧化物的机制。这项工作建立了以下内容：（1）荧光团的吸收和发射能量不受硝基氧取代基存在的影响，从加合物观察到的残余发射来自荧光团的局部激发单线态，不是来自电荷重组；(2) 氮氧化物分子内猝灭的速率常数 (k{sub q}) 很高 (10{sup 8}-10{sup 10} s{sup {minus}1}) 并且随着氮氧化物与荧光团距离的增加而显着降低-然而，在长达 12 {埃} 的距离内观察到相对较高的淬灭率 (>10{sup 8} s{sup {minus}1})；(3) 由于光谱重叠积分值较低，福斯特能量转移对淬灭没有显着贡献；(4) K{sub q}'s 不与 Dexter 重叠积分中溶剂相关的增加成比例增加，表明 Dexter 机制的能量转移不是猝灭的原因；(5) k{sub q}的值与计算的光

  DOI：

  10.1021/ja00176a038
• 作为产物：
  描述：

  阻聚剂701 、 1-萘甲酰氯 以 二氯甲烷 为溶剂， 反应 20.0h， 以962 mg的产率得到4-(1-萘甲酰氧基)-2,2,6,6-四甲基哌啶-1-氧自由基
  参考文献：
  名称：

  稳定的硝酰基自由基对激发单线态的分子内猝灭

  摘要：

  吸光度和稳态和时间分辨荧光测量被用来检查激发单线态猝灭的一系列氮氧化物荧光团加合物中的氮氧化物的机制。这项工作建立了以下内容：（1）荧光团的吸收和发射能量不受硝基氧取代基存在的影响，从加合物观察到的残余发射来自荧光团的局部激发单线态，不是来自电荷重组；(2) 氮氧化物分子内猝灭的速率常数 (k{sub q}) 很高 (10{sup 8}-10{sup 10} s{sup {minus}1}) 并且随着氮氧化物与荧光团距离的增加而显着降低-然而，在长达 12 {埃} 的距离内观察到相对较高的淬灭率 (>10{sup 8} s{sup {minus}1})；(3) 由于光谱重叠积分值较低，福斯特能量转移对淬灭没有显着贡献；(4) K{sub q}'s 不与 Dexter 重叠积分中溶剂相关的增加成比例增加，表明 Dexter 机制的能量转移不是猝灭的原因；(5) k{sub q}的值与计算的光

  DOI：

  10.1021/ja00176a038

文献信息

• The Spin Exchange of Nitroxide Radicals with Ni²⁺Ions in SDS Micellar Solutions
  作者：Masayuki Aizawa

  DOI：10.1246/bcsj.58.558

  日期：1985.2

  The spin-exchange rate of three kinds of hydrophobic nitroxide radicals with paramagnetic ions, Ni2+ ions, was measured in an aqueous sodium dodecyl sulfate (SDS) micellar solution at 30 °C. In the presence of SDS micelles, two of the three radicals had their spin-exchange rates accelerated, whereas the rate of the other radical was deaccelerated. These strange results were interpreted on the basis

  在 30 °C 的十二烷基硫酸钠 (SDS) 胶束水溶液中测量了三种疏水性氮氧自由基与顺磁性离子 Ni2+ 离子的自旋交换率。在存在 SDS 胶束的情况下，三个自由基中的两个自由基的自旋交换速率加快，而另一个自由基的速率减慢。这些奇怪的结果是根据 SDS 胶束中自由基的不同溶解位置来解释的。Ni2+ 离子在胶束表面的平移迁移率由加速系统中的自旋交换率估计。
• Measurements of Primary Radical Concentrations Generated by Pulsed Laser Photolysis Using Fluorescence Detection
  作者：Graeme Moad、Devon A. Shipp、Trevor A. Smith、David H. Solomon

  DOI：10.1021/jp990892t

  日期：1999.8.1

  Details of a novel technique for direct real-time measurement of the primary radical concentrations generated in pulsed laser photolysis (PLP) experiments ate presented. The method takes advantage of the large increase in fluorescence quantum yield that occurs when a nitroxide containing a suitable fluorophore couples with a carbon-centered radical. The technique is applied to PLP experiments which involve photolysis of azobisisobutyronitrile (AIBN) or azobis(methyl isobutyrate) (AIBMe) in the presence of 4-(1-naphthoyloxy)-2,2,6,6-tetramethylpiperidine-1-oxyl (NTEMPO). In these experiments, the method is shown to be capable of reliably measuring transient radical concentrations of less than 10(-7) M. Various side reactions that might complicate the technique are considered and shown not to be of significance. The concentration of radicals generated per pulse is shown to have a linear dependence on [AIBN], [AIBMe], and laser energy per pulse (and is shown to be independent of [NTEMPO]) over a wide range of conditions encompassing those typically encountered in PLP polymerization experiments. The concentration of radicals generated per pulse increases with increasing temperature, reflecting changes in the quantum yield for radical generation. The rate of intramolecular fluorescence quenching of NTEMPO in benzene was determined to be in the range 2-4 x 10(10) s(-1).
• The philicity of tert-butoxy radicals. What factors are important in determining the rate and regiospecificity of tert-butoxy radical addition to olefins?
  作者：Michael J. Jones、Graeme Moad、Ezio Rizzardo、David H. Solomon

  DOI：10.1021/jo00268a022

  日期：1989.3
• Fluorescent polyolefins by free radical post-reactor modification with functional nitroxides
  作者：Francesca Cicogna、Serena Coiai、Calogero Pinzino、Francesco Ciardelli、Elisa Passaglia

  DOI：10.1016/j.reactfunctpolym.2012.06.021

  日期：2012.10

  The 4-(1-naphthoate)-2,2,6,6-tetramethylpiperidine-1-oxyl (NfO-TEMPO) has been synthesized and successfully grafted in the melt onto a random poly(ethylene-co-1-ottene) copolymer. Functionalized polyolefins have been prepared by coupling reaction between NfO-TEMPO free radicals and macroradicals which have been formed by H-abstraction induced by the presence of a peroxide. In order to deepen insight into the functionalization mechanism, the reaction has been investigated by Electron Paramagnetic Resonance (EPR). EPR spectra collected during the reaction run, have evidenced the decrease of TEMPO signal as a consequence of temperature increasing. This decrease has been attributed to the formation of a covalent bond between macroradicals and nitroxide free radical. The resulting functionalized polyolefins. PO-g-(NfO-TEMPO), have been characterized by FT-IR and H-1 NMR which has allowed to evaluate their functionalization degree, whereas UV-Vis and fluorescence spectroscopy have been used to investigate their optical properties. The comparison with low molecular weight model compounds, has allowed to state that our methodology can be conveniently adopted to prepare fluorescent polyolefins where the optical properties of the chromophore has been completely transferred to polymer backbone both in solution and in the condensed phase. (C) 2012 Elsevier Ltd. All rights reserved.