3-hydroxy-phenyloxyl | 24856-47-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 3-hydroxy-phenyloxyl
• 英文别名: 3-hydroxyphenoxyl radical；Resorcinol radical；3-Hydroxy-phenoxy-radikal；m-Dihydroxybenzol-Radikal；3-Hydroxyphenoxy-Radikal；3-Hydroxyphenoxylradikal；Meta-benzosemiquinone
• CAS: 24856-47-1
• 化学式: C₆H₅O₂
• 分子量: 109.105
• InChiKey: GYUBJLLHIYIXSA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  21.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  n-butyl radical 、 3-hydroxy-phenyloxyl 以 various solvent(s) 为溶剂， 生成 4-正丁氧基苯酚
  参考文献：
  名称：

  二酚自由基阳离子和半醌自由基作为从儿茶酚、间苯二酚和对苯二酚到母体溶剂自由基阳离子的自由电子转移的直接产物

  摘要：

  在邻苯二酚、间苯二酚和对苯二酚在正丁基氯中的溶液的脉冲辐解中，观察到二羟基苯自由基阳离子（40%）和半醌自由基（60%）是电子从溶剂母离子转移到溶质。这可以用几乎每次反应物的自由电子转移成功来解释，在所研究的二羟基苯的情况下，这涉及飞秒分子动力学效应。C-OH 键的旋转导致分子通过瞬态构象循环，也表现出不同的电子分布。从更化学的角度来看，二酚自由基阳离子代表了氧化半醌自由基形成的第一个也是迄今为止未知的中间体。

  DOI：

  10.1039/b205771a
• 作为产物：
  描述：

  anion of resorcinol 在 二氧化氮 作用下， 以 水 为溶剂， 生成 3-hydroxy-phenyloxyl
  参考文献：
  名称：

  取代基对二氧化氯，二氧化氮和三氧合硫酸根（1-）自由基对酚的单电子氧化速率的影响

  摘要：

  DOI：

  10.1021/j100408a063

文献信息

• Stopped-Flow and Spectrophotometric Study on Radical Scavenging by Tea Catechins and the Model Compounds.
  作者：Yasushi SENBA、Tsukasa NISHISHITA、Keiko SAITO、Hiroe YOSHIOKA、Hisashi YOSHIOKA

  DOI：10.1248/cpb.47.1369

  日期：——

  Radical scavenging of four tea catechins, (-)-epicatechin (EC), (-)-epigallocatechin (EGC), (-)-epicatechin gallate (ECg) and (-)-eppigallocatechin gallate (EGCg), and the model compounds of their partial structure was examined against the 1, 1-diphenyl-2-picrylhydrazyl (DPPH) radical using stopped-flow and spectrophotometric methods. The number of DPPH radicals scavenged by a polyphenol molecule was larger than that of phenolic hydroxyl groups, suggesting that hydrogens which bond directly to the aromatic ring can also participate in radical scavenging. A model for the scavenging reaction was proposed in which the reaction proceeded with successive dehydrogenation from a polyphenol molecule. Analysis of the second order reaction rate constants and the activation parameters between DPPH and polyphenol at the early stage of the reaction showed that the values depended on the number of phenolic hydroxyl groups and their mutual position. Contribution of the A ring of catechins to the rate constants was estimated to be far smaller than that from the B ring. In the EGCg molecule, the B ring and the gallate group were not independent, but acted as a single group for DPPH radical scavenging.

  对四种茶多酚(-)-表儿茶素(EC)、(-)-表没食子儿茶素(EGC)、(-)-表儿茶素没食子酸酯(ECg) 和(-)-表没食子儿茶素没食子酸酯(EGCg)及其部分结构的模型化合物， 用停流法和分光光度法研究了它们对1,1-二苯基-2-苦基肼基(DPPH)自由基的清除作用，发现一个多酚分子清除DPPH自由基的能力比羟基的数目强，说明直接与芳香环相连的氢原子也能参与自由基清除反应。提出了一个多酚分子连续脱氢的清除反应模型。研究了早期反应阶段DPPH和多酚的二级反应速率常数和活化参数，发现其数值与酚羟基数目及其相对位置有关。儿茶素A环对速率常数的贡献比B环小得多。在EGCg分子中，B环和没食子酸基团不是独立的，而是作为一个整体对DPPH自由基起清除作用。
• Reaction of tert-butoxy radicals with phenols. Comparison with the reactions of carbonyl triplets
  作者：P. K. Das、M. V. Encinas、S. Steenken、J. C. Scaiano

  DOI：10.1021/ja00404a030

  日期：1981.7

  Tert-butoxy radicals generated in the photodecomposition of di-tert-butyl peroxide react efficiently with phenols to yield the corresponding phenoxy radicals. Typical rate constants in benzene at 22/sup 0/C are 3.3 x 10/sup 8/ and 1.6 x 10/sup 9/ M/sup -1/ s/sup -1/ for phenol and p-methoxyphenol, respectively. The process is considerably slower in polar solvents; e.g., when pyridine is used as cosolvent

  二叔丁基过氧化物光分解中产生的叔丁氧基自由基与酚类有效反应生成相应的苯氧基自由基。苯中的典型速率常数在 22/sup 0/C 时分别为 3.3 x 10/sup 8/ 和 1.6 x 10/sup 9/ M/sup -1/ s/sup -1/ 苯酚和对甲氧基苯酚。该过程在极性溶剂中要慢得多；例如，当使用吡啶作为助溶剂时，苯酚的速率常数下降到 4.1 x 10/sup 6/ M/sup -1/ s/sup -1/，这是由于强氢键降低了酚类 OH 的反应性团体。同位素效应 (H/D) 通常在 3 到 5 的范围内。5个数字，4个表格。
• Factors Influencing the Antioxidant Activities of Phenols by an Ab Initio Study.
  作者：Shogo Tomiyama、Shogo Sakai、Tomihiro Nishiyama、Fukiko Yamada

  DOI：10.1246/bcsj.66.299

  日期：——

  An ab initio molecular orbital theory has been applied to the elucidation of the hydrogen abstraction mechanism of phenolic antioxidants in the chain process of autoxidations. The optimum structures of o-, m-, and p-substituted phenols, of peroxides, and of those compounds in the transition states were obtained with a Hartree-Fock/STO-3G basis set. From the values of the enthalpy (ΔH), activation (Ea), and OH bond dissociation (D(O–H)) energies obtained, it was found that these three parameters indicate a good relationship with each other; particularly, the relation between the ΔH and Ea values follows the Evans-Polanyi rule. The electron-releasing substituents in the o- and p-positions in phenols decrease the activation parameters for hydrogen abstraction, while those in the m-position increase. The electron densities on the ipso-carbon, oxygen, and hydrogen of the OH substituent and their bond populations are obtained. Variations of the electron densities from the reactants to the transition states lead to a clarification of the reaction mechanism as an antioxidant. Namely, the gain or loss of electrons in the reaction states may be correlated to the experimental data, 13C chemical shifts of the ipso-carbon of the OH substituent, and the values of the induction period as an antioxidant activity.

  从头算分子轨道理论已被应用于阐明酚类抗氧化剂在自氧化链式反应中的夺氢机理。通过使用哈特里-福克/STO-3G基组，得到了邻、间、对位取代酚、过氧化物以及过渡态化合物的优化结构。从获得的焓变（ΔH）、活化能（Ea）和羟基键解离能（D(O–H)）值来看，这三个参数之间显示出良好的相关性；特别是ΔH和Ea值之间的关系遵循埃文斯-波拉尼规则。酚类化合物中邻位和对位上的供电子取代基会降低夺氢反应的活化参数，而间位上的取代基则会提高这些参数。计算得到了OH取代基的ipso碳、氧、氢上的电子密度及其键的布居数。从反应物到过渡态电子密度的变化有助于阐明抗氧化剂反应机理。即，反应态中电子的增益或损失可能与实验数据、OH取代基的ipso碳的13C化学位移以及抗氧化活性的诱导期值相关联。
• Reduction Potentials and Kinetics of Electron Transfer Reactions of Phenylthiyl Radicals:  Comparisons with Phenoxyl Radicals
  作者：D. A. Armstrong、Qun Sun、R. H. Schuler

  DOI：10.1021/jp960165n

  日期：1996.1.1

  The reduction potentials relative to the standard hydrogen electrode (SHE) for a number of para-substituted phenylthiyl radicals (E°(p-XC6H4S•/p-XC6H4S-)) have been derived from pulse radiolytic studies of electron transfer equilibria which compare their values to those of radicals of known reduction potentials. A ladder combining the reduction potentials for both phenylthiyl and phenoxyl radicals has

  相对于为多个对位取代phenylthiyl自由基（标准氢电极（SHE）还原电位ë °（p -XC 6 ħ 4小号• / p -XC 6 ħ 4小号- ））已经被从脉冲辐解衍生研究电子转移平衡，将其值与已知还原电位的自由基的值进行比较。建立了结合了苯基硫基和苯氧基自由基还原电位的阶梯。这些还原电位已被证明是自洽的，并且介于p的还原电位之间-苯并半醌基阴离子为0.02 V，苯氧基为0.79V。还原电位随着对位取代基的给电子力的增加而降低。然而，对苯硫基自由基的取代作用比对它们的氧类似物的作用要弱得多。这些观察结果表明，硫原子与芳环系统之间的电子相互作用远小于氧原子所发生的电子相互作用。用马库斯理论检验电子传输速率表明，p -XC 6 H 4 O •和p -XC 6 H 4 S •的重组能自由基同样受H，CH 3和CH 3 O取代的影响。然而，重组能大幅提高用于h 2 N和O -位取代基具有其效果是为要少得多p
• The effect of the medium polarity on the mechanism of the reaction of hydroxybenzenes with hydrazyl radical in aprotic solvents
  作者：N. I. Belaya、A. V. Belyj、O. M. Zarechnaya、I. N. Scherbakov、V. M. Mikhalchuk、V. S. Doroshkevich

  DOI：10.1134/s1070363217040053

  日期：2017.4

  Mechanisms of the reaction of di- and trihydroxybenzenes with 2,2′-diphenyl-1-picrylhydrazyl (stable radical) in aprotic media of different polarity have been elucidated by experimental and quantum-chemical methods. Kinetic, stoichiometric, and activation parameters of the reaction have been determined. In benzene (nonpolar solvent), the studied reaction occurs via the hydrogen atom transfer mechanism;

  通过实验和量子化学方法阐明了二羟基苯和三羟基苯与2,2'-二苯基-1-吡啶并肼基（稳定基团）在不同极性的非质子介质中的反应机理。已经确定了反应的动力学，化学计量和活化参数。在苯（非极性溶剂）中，所研究的反应是通过氢原子转移机理发生的。在电离能力弱的极性溶剂（即DMSO）中，反应主要是通过电子和质子转移的更快机理进行的。