N-tert-butyl-N-(1-phenylethyl)nitroxide | 21894-27-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-tert-butyl-N-(1-phenylethyl)nitroxide
• 英文别名: t-butyl-1-methylbenzyl nitroxide；α-methylbenzyl-tert-butylaminoxyl；α-methylbenzyl tert-butyl nitroxide；Benzyl-α-methyl-tert.-butylnitroxid；tert.-Butyl-1-phenethylnitroxid-Radikal
• CAS: 21894-27-9
• 化学式: C₁₂H₁₈NO
• 分子量: 192.281
• InChiKey: XDQNSOQOXQOUNR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  4.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-tert-butyl-N-(1-phenylethyl)nitroxide 在 维生素 C 作用下， 以 phosphate buffer 为溶剂， 生成 苯甲胺,N-(1,1-二甲基乙基)-N-羟基-a-甲基-
  参考文献：
  名称：

  Comparative Metabolism of N-tert-Butyl-N-[1-(1-oxy-pyridin-4-yl)-ethyl]- and N-tert-Butyl-N-(1-phenyl-ethyl)-nitroxide by the Cytochrome P450 Monooxygenase System

  摘要：

  The use of spin-trapping agents for a direct ESR detection of (OH)-O-. in biological systems is limited by the low stability of the hydroxyl radical-derived nitroxides. Among the various probes used for trapping of (OH)-O-., DMSO has proven to be highly efficient. The reaction between (OH)-O-. and DMSO yields methyl radical (CH3.), which can react with N-tert-butyl-alpha-phenylnitrone (PBN) and alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone (POBN) to form stable, ESR-detectable nitroxides. The latter approach has been successfully used in in vivo experiments for analysis of (OH)-O-.; in these experiments, POBN/.CH3 and PBN/.CH3 were detected in the bile duct and the urine of the treated animals. However, the sites of generation of (OH)-O-. produced in vivo are unknown. Currently, no ESR data is available for the formation of (OH)-O-. in liver of animals subjected to oxidative stress. Since nitroxides containing aromatic rings are likely to be substrates of cytochrome P450, experiments were carried out for assessing the ability of the cytochrome P450 monooxygenase system to metabolize PBN/.CH3 and POBN/.CH3, respectively. In the presence of NADPH, rat liver microsomes catalyzed the reduction of POBN/.CH3 to the corresponding hydroxylamine (POBN/CH3), while PBN/.CH3 was metabolized without accumulation of its hydroxylamine form (PBN/CH3). The metabolism of PBN/.CH3 was inhibited by 4-methylpyrazole and ketoconasole, suggesting that cytochrome P450-catalysis was required for the consumption of this nitroxide. Under anaerobic conditions, both the nitroxide and hydroxylamine forms of PBN/CH3 were metabolized, implying that these adducts may undergo reductive cytochrome P450-catalyzed biotransformation. On the basis of the susceptibility of PBN/.CH3 to undergo irreversible metabolic transformation, it is discussed that POBN may prove to be a more efficient spin-trapping agent for the in vivo detection of .OH.

  DOI：

  10.1021/tx025510g
• 作为产物：
  描述：

  N-叔丁基-Alpha-苯基硝酮 在 phosphate buffer 、 维生素 C 作用下， 以 乙醚 为溶剂， 反应 0.17h， 生成 N-tert-butyl-N-(1-phenylethyl)nitroxide
  参考文献：
  名称：

  An ESR and HPLC-EC Assay for the Detection of Alkyl Radicals

  摘要：

  The correlation of lipid peroxidation with release of alkanes (RH) is considered a noninvasive method for the in vivo evaluation of oxidative stress. The formation of RH is believed to reflect a lipid hydroperoxide (LOOH)-dependent generation of alkoxyl radicals (LO.) that undergo, beta -scission with release of alkyl radicals (R-.). Alternatively, R-. could be spin-trapped with a nitrone before the formation of RH and analyzed by ESR. Extracts from the liver and lung of CCl4- and asbestos-treated rats that were previously loaded with nitrones exhibited ESR spectra suggesting the formation of iso-propyl, n-butyl, ethyl, and pentyl radical-derived nitroxides. In biological systems, various nitroxides with indistinguishable ESR spectra could be formed. Hence, experiments with N-tert-butyl-alpha -phenylnitrone (PBN) for spin trapping of R-. were carried out in which the nitroxides formed were separated and analyzed by HPLC with electrochemical detection (EC). The C1-5 homologous series of PBN nitroxides and hydroxylamines were synthesized, characterized by ESR, GC-MS, and HPLC-EC, and used as HPLC standards. For in vivo generation and spin trapping of R-., rats were loaded with CCl4 and PBN. The HPLC-EC chromatograms of liver extracts from CCl4-treated rats demonstrated the formation of both the nitroxide and hydroxylamine forms of PBN/(CCl3)-C-., as well as the formation of a series of unidentified PBN nitroxides and hydroxylamines. However, formation of PBN adducts with retention times similar to these of the PBN/C2-5 derivatives was not observed. In conclusion, we could not correlate the production of PBN-detectable alkyl radicals with the reported CCl4-dependent production Of C1-5 alkanes. We speculate that the major reason for this is the low steady-state concentrations of R-. produced because only a small fraction of LO. undergo,beta -scission to release R-..

  DOI：

  10.1021/tx015507h

文献信息

• High static pressure alters spin trapping rates in solution. Dependence on the structure of nitrone spin traps
  作者：Yoshimi Sueishi、Daisuke Yoshioka、Chiharu Yoshioka、Shunzo Yamamoto、Yashige Kotake

  DOI：10.1039/b515682c

  日期：——

  Using a competitive spin trapping method, relative spin trapping rates were quantified for various short-lived radicals (methyl, ethyl, and phenyl radicals). High static pressure was applied to the competitive spin-trapping system by employing high-pressure electron spin resonance (ESR) equipment. Under high pressure (490 bar), spin trapping rate constants for alkyl and phenyl radicals increased by

  使用竞争性自旋俘获方法，对各种短寿命自由基（甲基，乙基和苯基）的相对自旋俘获速率进行了定量。通过使用高压电子自旋共振（ESR）设备，将高静压应用于竞争性自旋捕集系统。在高压（490 bar）下，烷基和苯基自由基的自旋俘获速率常数增加了10％至40％，并且该增加取决于硝酮自旋阱的结构。当叔丁基（4-吡啶基亚甲基）胺N-氧化物（4-POBN）用作自旋阱时，可获得最大的增加。对于四个POBN系统，两个自旋捕获反应的激活体积（DeltaDeltaV（双匕首））计算为-17-（-9）cm（3）mol（-1）。
• Role of Radical Species in Salicylaldiminato Ni(II) Mediated Polymer Chain Growth: A Case Study for the Migratory Insertion Polymerization of Ethylene in the Presence of Methyl Methacrylate
  作者：Franz Ölscher、Inigo Göttker-Schnetmann、Vincent Monteil、Stefan Mecking

  DOI：10.1021/jacs.5b08612

  日期：2015.11.25

  Ni(II) insertion polymerization catalysts toward methyl methacrylate (MMA). We shed light on this issue by a combination of comprehensive mechanistic NMR and EPR studies, isolation of a key Ni(I) intermediate, and pressure reactor studies with ethylene and MMA, followed by detailed polymer analysis. An interlocking mechanistic picture of an insertion and a free radical polymerization is revealed. Both

  迄今为止，中性 Ni(II) 插入聚合催化剂对甲基丙烯酸甲酯 (MMA) 的行为尚无定论且部分矛盾。我们通过综合机械 NMR 和 EPR 研究、关键 Ni(I) 中间体的分离以及乙烯和 MMA 的压力反应器研究的结合，以及详细的聚合物分析，阐明了这个问题。揭示了插入和自由基聚合的互锁机制图。两种聚合同时进行（25 bar 乙烯，纯 MMA，70 °C）；然而，链增长周期彼此独立，因此仅获得均质 PE 和均质 PMMA 的物理混合物。Ni-C 键断裂被排除为自由基来源。相反，不稳定的芳基膦配体中的均裂 PC 键断裂和低价 Ni(0/I) 物质与特定碘取代的 N^O (Ar-I) 配体的反应显示出引发自由基 MMA 聚合。催化剂前体或活性中间体的几种还原消除分解途径显示出形成低价镍物种。这些途径之一是通过中间 (N^O)Ni(I) 形成的双分子还原偶联。这些中间体 Ni(I) 物种可以通过用有机自由基源捕获、形成插入聚合活性
• ¹H NMR of (α-Substituted benzyl-<i>t</i>-butyl)hydroxylamines and EPR of Their Oxidized Forms
  作者：Gatherina T. Migita、Masaharu Nakayama、Makoto Takeuchi、Kotaro Ogura

  DOI：10.1246/cl.1991.737

  日期：1991.5

  1H NMR study of several (benzyl-t-butyl)hydroxylamine derivatives (BBHA) was performed, which were obtained through the addition of Grignard agents to α-phenyl-N-t-butylnitrone (PEN) or the reduction of PEN. Concomitantly, EPR of their oxidized forms (nitroxide radicals, BEN) was measured. It was proved that the joint application of 1H NMR and EPR provides decisive evidences to assign the α-substituents.

  对几种（苄基-t-丁基）羟胺衍生物（BBHA）进行了1H NMR研究，这些衍生物是通过Grignard试剂与α-苯基-N-t-丁基亚胺（PEN）反应或对PEN进行还原获得的。同时，测量了它们的氧化形式（亚硝基自由基，BEN）的EPR。研究证明，1H NMR与EPR的联合应用为α-取代基的分配提供了决定性证据。
• Gold nanoparticle-initiated free radical oxidations and halogen abstractions
  作者：Petre Ionita、Marco Conte、Bruce C. Gilbert、Victor Chechik

  DOI：10.1039/b711573c

  日期：——

  containing active hydrogen atoms, such as amines and phosphine oxides. Nanoparticles protected by stronger bound ligands (e.g., thiols) were inactive in these reactions. We also found that gold nanoparticles are able to abstract a halogen atom from the halogenated compounds, presumably due to the high affinity of gold metal for halogens. Reaction of Au nanoparticles with chloroform showed an unusual

  我们报告了使用EPR光谱和自旋捕获技术来检测在金纳米粒子的存在下形成的自由基中间体。发现被膦和胺保护的金纳米颗粒会引发空气中含有活性氢原子的有机底物的空气氧化，例如胺和氧化膦。受较强结合的配体（例如硫醇）保护的纳米颗粒在这些反应中没有活性。我们还发现，金纳米颗粒能够从卤代化合物中提取卤素原子，这可能是由于金金属对卤素的高度亲和力所致。金纳米粒子与氯仿的反应显示出不同寻常的反同位素效应。当金纳米粒子与CDCl（3）而不与CHCl（3）混合时，观察到三氯甲基自旋加合物。
• Reactions of ozonate and superoxide radical anions
  作者：Alexander R. Forrester、Vemishetti Purushotham

  DOI：10.1039/f19878300211

  日期：——

  Potassium ozonate has been prepared by reaction of ozone with potassium superoxide dispersed in Freon-12. Orange solutions of potassium ozonate in benzene or toluene containing 18-crown-6 react with nitrone traps to give spin adducts mainly derived from the oxide radical anion, which is a decomposition product of the ozonate radical anion. With 2-methyl-2-nitrosopropane in toluene solution the ozonate

  臭氧化钾是通过使臭氧与分散在氟利昂12中的超氧化钾反应制得的。含氧氮酸钾在苯或甲苯中的18-crown-6的橙色溶液与硝酮阱反应，生成主要衍生自氧化物氧自由基阴离子的自旋加合物，该氧化物是臭氧氧自由基阴离子的分解产物。用在甲苯溶液中的2-甲基-2-亚硝基异丙基丙烷，该膦酸酯产生五个氮氧化物自由基，在该氮氧化物自由基的形成中又牵涉到氧化物自由基阴离子。与亚硝基苯发生电子转移。描述了与超氧化物的可比反应。