α-Benzoyloxybenzylnitroxid | 21894-30-4

• 英文名称: α-Benzoyloxybenzylnitroxid
• CAS: 21894-30-4
• 化学式: C₁₈H₂₀NO₃
• 分子量: 298.362
• InChiKey: MEIYJHABGLYJOY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  N-叔丁基-α-苯基硝酮 、 过氧化苯甲酰 在 2,4,6-tri-(p-methoxyphenyl) pyrylium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 生成 α-Benzoyloxybenzylnitroxid
  参考文献：
  名称：

  通过非常规机理从N-叔丁基-α-苯基硝基（PBN）和4,5-二氢-5,5-二甲基吡咯1-氧化物（DMPO）生成酰氧基自旋加合物

  摘要：

  N-叔丁基-α-苯基硝酮（PBN）与羧酸的反应已被研究。可以区分出两种机理：通过光化学产生的激发态氧化PBN生成PBN⁺+，随后与RCOOH反应，或者RCOOH加成到PBN上形成羟胺衍生物，随后由弱氧化剂热氧化。后一序列是Forrester-Hepburn机理。在该机理中，2+和4都不作为氧化剂有效，而溴可以被使用。因此，只有氧化还原电位大于0.1 V（SCE）的氧化剂才足以氧化中间体羟胺。这种行为与羟胺的氧化还原反应性一致。对于环状硝酮，4,5-二氢-5,5-二甲基吡咯1-氧化物（DMPO），通过光化学途径制备了酰氧基自由基自旋加合物。过二苯甲酰与PBN反应生成PhCOO⁻PBN⁺+不通过添加的PhCOOH催化。可以表明，PhCOO⁻PBN⁺+的生成速率与过二苯甲酰的热分解速率相符。因此，过二苯甲酰不支持Forrester-Hepburn机理，与其氧化还原电位约为-0.2 V一致。

  DOI：

  10.1039/a701479a

文献信息

• Décomposition du peroxyde de benzoyle dans les mélanges benzéne/X-4 pyridines (X = CH3, H, CN). etude cinétique et influence des substituants sur la réactivité nucléophile et radicalaire de l'atome d'azote
  作者：S Vidal、J Court、J.M Bonnier

  DOI：10.1016/s0040-4020(01)91326-2

  日期：1984.1

  pyridine ring upon the decomposition kinetics of benzoyl peroxide in 4-X pyridine/benzene binary mixtures(X = CH3,H,CN) has been studied. The second-order rate constant for the pyridine-induced decomposition was 2xl0-6l mol-1 s-1 and in 4-methylpyridine it was l0-5 l mol-1 s-1, a five-fold increase, whereas there was no nucleophilic attack on the peroxide oxygen atoms of benzoyl peroxide by 4-cyanopyridine

  研究了吡啶环中的4-取代基对4-X吡啶/苯二元混合物（X = CH 3，H，CN）中过氧化苯甲酰分解动力学的影响。吡啶诱导的分解的二级速率常数为2xl0 -6 l mol -1 s -1，在4-甲基吡啶中为10 -5 l mol -1 s -1，增加了五倍，而4-氰基吡啶对苯甲酰过氧化物的过氧化物氧原子没有亲核攻击。自由基引起的4-氰基吡啶的分解的惊人的高增加可能是由于苯基自由基对吡啶环的氮原子的攻击所致，其中1-苯基吡啶基自由基被氰基稳定化了。
• Spin Trapping of Phosphorus-Centered Radicals Produced by the Reactions of Dibenzoyl Peroxide with Organophosphorus Compounds
  作者：Yoshimi Sueishi、Yuzo Miyake

  DOI：10.1246/bcsj.70.397

  日期：1997.2

  means of an ESR technique combined with spin trapping. The intermediate phosphorus-centered radicals were trapped by N-benzylidene-t-butylamine N-oxide (PBN) and 5,5-dimethyl-1-pyrroline N-oxide (DMPO). The spin adducts with a characteristic hyperfine coupling constant (hfcc) due to a phosphorus atom were observed. From identification of trapped radicals, possible mechanisms of the reactions have been

  已经通过结合自旋捕获的 ESR 技术研究了过氧化二苯甲酰 (BPO) 与有机磷化合物的反应。中间体以磷为中心的自由基被 N-亚苄基-叔丁胺 N-氧化物 (PBN) 和 5,5-二甲基-1-吡咯啉 N-氧化物 (DMPO) 捕获。观察到由于磷原子而具有特征超精细耦合常数 (hfcc) 的自旋加合物。从被困自由基的识别中，已经提出了反应的可能机制。β-氢和磷原子引起的 hfccs 对磷酰基-PBN 自旋加合物表现出很大的温度依赖性，而对于膦酰基-PBN 自旋加合物，依赖性很小。基于 P 和 H hfccs，讨论了 PBN 和 DMPO 捕获的加合物的构象位置。
• Abe, Yukino; Seno, Shin-ya; Sakakibara, Kazuhisa, Journal of the Chemical Society. Perkin transactions II, 1991, # 6, p. 897 - 903
  作者：Abe, Yukino、Seno, Shin-ya、Sakakibara, Kazuhisa、Hirota, Minoru

  DOI：——

  日期：——
• Mass Spectrometry and Electron Paramagnetic Resonance Study of Free Radicals Spontaneously Formed in Nitrone−Peracid Reactions
  作者：Hong Sang、Edward G. Janzen、Brian H. Lewis

  DOI：10.1021/jo952031w

  日期：1996.1.1

  Reactions of spin traps (C-phenyl N-tert-butyl nitrone (PEN) and 5,5-dimethyl-2-phenyl-1-pyrroline N-oxide (2-Ph-DMPO)) with peracids have been investigated by both mass spectrometry (MS) and electron paramagnetic resonance(EPR). The peracids m-chloroperbenzoic acid, perbenzoic acid, and perpropionic acid, which can be considered models of biological peracids produced during lipid peroxidation, were found to react with spin traps to spontaneously produce significant amount of aminoxyl radicals, The radical products, as well as the nonradical products were detected and their structures identified by EPR and/or MS. Mechanisms for the formation of these products are proposed.
• Synthesis of a Novel Nitrone, 2-Phenyl-5,5-dimethyl-1-pyrroline N-Oxide (nitronyl-13C), for Enhanced Radical Addend Recognition and Spin Adduct Persistence
  作者：Edward G. Janzen、Yong-Kang Zhang、D. Lawrence Haire

  DOI：10.1021/ja00088a009

  日期：1994.5

  Synthesis and spin trapping chemistry of the new C-13-labeled cyclic nitrone, 2-phenyl-5,5-dimethyl-1-pyrroline N-oxide (nitronyl-C-13), is described. A total of 15 carbon- and oxygen-centered radical adducts were prepared and their electron paramagnetic resonance (EPR) spectral parameters examined in organic as well as aqueous solutions. All the radical spin adducts derived from the novel nitrone displayed a well-resolved triplet of doublets in the EPR spectra. The alpha-C-13 hyperfine splitting is a good indicator for the chemical structure of the added radical and varies from around 3.2 to 6.2 G. Free radicals are spin trapped at rates that are quite comparable to those observed with C-phenyl-N-tert-butylnitrone (PBN). The main advantage, however, is the enhanced persistence of its radical spin adducts. For this reason the title nitrone holds promise as a biological spin trapping agent because spin adduct decay during metabolism or isolation often governs the success or failure of a given experiment.