2,6-二甲氧基苯氧基 | 15773-12-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2,6-二甲氧基苯氧基
• 英文名称: 2,6-Dimethoxyphenoxyl radical
• 英文别名: 2,6-dimethoxy-phenyloxyl
• CAS: 15773-12-3
• 化学式: C₈H₉O₃
• 分子量: 153.158
• InChiKey: RRUVRDMLPKYWJQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.85
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  38.36
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2,6-二甲氧基苯氧基 在 ferrocenedicarboxylate 作用下， 以 水 为溶剂， 生成 2,6-Dimethoxyphenol anion
  参考文献：
  名称：

  Use of the Hammett correlation and .delta.+ for calculation of one-electron redox potentials of antioxidants

  摘要：

  Spectral, acid-base, and redox properties of methoxyphenoxyl radicals were determined in aqueous solutions by pulse radiolysis. Except for 2,6-dimethoxyphenoxyl, with lambda(max) < 300 nm, methoxyphenoxyl radicals absorb in the visible spectrum, with high molar absorptivities. From the effect of ionic strength on the rate of radical decay, a pK(a) < 2 was estimated for the deprotonation of phenolic radical cations. The oxidation potentials of methoxyphenols were determined from the electron-transfer equilibria with inorganic redox standards. The largest effect of methoxy groups on oxidation potential was observed for 2,6-dimethoxyphenol, E7 = 0.58 V vs NHE, whereas the effect of meta substitution was minimal for 3,5-dimethoxyphenol, E7 = 0.85 V, yet this was 0.12 V lower than the measured E7 of 0.97 V for unsubstituted phenol. The reduction potential E7 of methoxyphenoxyl radicals satisfies the Hammett correlation using Brown sigma+ substituent constants, as do other monosubstituted phenoxyls if the additivity of sigma+ values is assumed and the state of protonation of the substituents is taken into consideration. The derived sigma+(CH3O)m value of -0.14, in contrast to reported positive values, indicates the contribution of the methoxy group, even in the meta position, to charge delocalization and resonant stabilization of the phenoxyl radical. The contribution of the ring structure to more negative sigma+ values was observed, as expected. Use of the Hammett correlation is suggested for rapid estimation and accurate calculation of the redox potentials of polysubstituted phenolic antioxidants.

  DOI：

  10.1021/j100179a054
• 作为产物：
  描述：

  2,6-二甲氧基苯酚 在 cumyloxyl radical 作用下， 以 四氯化碳 为溶剂， 生成 2,6-二甲氧基苯氧基
  参考文献：
  名称：

  分子内氢键合泛醇-0 和其他（多）甲氧基苯酚的氢原子提取动力学

  摘要：

  通过激光闪光光解研究了甲氧基取代对参与分子内氢键的酚氢原子被叔丁氧基和枯氧基自由基提取的影响。还通过密度泛函理论 (DFT) 方法对甲氧基自由基和 2-甲氧基苯酚进行了过渡态计算。与分子间氢键合的分子相比，从分子内氢键合的甲氧基苯酚中提取氢原子非常容易。在具有不同氢键接受特性的六种溶剂中研究的动力学溶剂效应对邻甲氧基苯酚的氢原子夺取反应的影响小于非氢键苯酚，并且与进一步的甲氧基取代无关。

  DOI：

  10.1021/ja9937674

文献信息

• Oxidation of phenols employing polyoxometalates as biomimetic models of the activity of phenoloxidase enzymes
  作者：Carlo Galli、Patrizia Gentili、Ana Sofia Nunes Pontes、Jose A. F. Gamelas、Dmitry V. Evtuguin

  DOI：10.1039/b703178e

  日期：——

  the experimental oxidation data. A sizeable value for the reorganisation energy (λ) was accordingly obtained. The slightly stronger oxidant SiW11Mn resulted to be more reactive than SiW11V by ca. two powers of magnitude. Our scrutiny of the reactive behaviour of the two POMs towards phenols may provide a model of interpretation for the phenoloxidase activity of the laccase enzymes, a class of multicopper

  取代基氧化的动力学研究 酚类与任一钒（V）polyoxotungstate，[α-SIV V w ^ 11 ö 40 ] 5-（即硅钨酸11 V），或锰（III）polyoxotungstate，[α-硅锰III W¯¯ 11（H 2 O）O- 39 ] 5-（即硅钨酸11的Mn），已经进行了。因为多金属氧酸盐SiW 11 V和SiW 11 Mn化合物的氧化还原电位，即。POM为0.67和0.76 V /NHE以及酚醛底物的电压分别在0.4-0.9 V /NHE 在 水，所产生的氧化反应是外能的或轻微的内能的。的反应性氧化作用 的替代 酚类通过SiW 11 V，在50°C的缓冲水溶液（pH = 4）中，发现与取代基的σ +参数相关，产生与电子共振的冈本-布朗ρ值（即-3.1）决定速率的电子转移途径的要求。的微不足道的价值溶剂用SiW 11 V氧化p -MeO-苯酚获得动力学同位素效应（k H
• Absolute Rate Constants for Some Intermolecular Reactions of α-Aminoalkylperoxyl Radicals. Comparison with Alkylperoxyls
  作者：Jacques Lalevée、Xavier Allonas、Jean-Pierre Fouassier、K. U. Ingold

  DOI：10.1021/jo800925g

  日期：2008.9.1

  alpha-aminoalkylperoxyl radicals have been generated by 355 nm laser flash photolysis (LFP) of oxygen-saturated di-tert-butyl peroxide containing mono-, di-, and trialkylamines and a dialkylarylamine. All these peroxyls possess absorptions in the near-UV (strongest for the trialkylamine-derived peroxyls) which permits direct monitoring of the kinetics of their reactions with many substrates. The measured rate constants

  通过355 nm的含单，二和三烷基胺和二烷基芳基胺的氧饱和二叔丁基过氧化物的355 nm激光快速光解（LFP）产生了七个α-氨基烷基过氧自由基。所有这些过氧化物都具有在近紫外光（对于三烷基胺衍生的过氧化物最强）的吸收，从而可以直接监测其与许多底物的反应动力学。从一些酚中提取氢原子并将氧原子转移至三苯基膦的测得的速率常数表明，所有七个α-氨基烷基过氧基均对每种特定底物具有相似的反应性。更重要的是，与烷基过氧基的文献数据比较表明，α-氨基烷基过氧基和这些烷基过氧基具有基本相同的反应性。
• Kinetic and thermodynamic parameters for the equilibrium reactions of phenols with the dpph? radical
  作者：Mario C. Foti、Carmelo Daquino

  DOI：10.1039/b606322e

  日期：——

  The kinetics and energetics of the reversible reaction of phenols with the dpph. radical have been studied; steric shielding of the divalent N by the o-NO2 in dpph. seems to be the main cause of the entropic barriers of this reaction.

  酚类与dpph可逆反应的动力学和能量学。激进分子已经被研究过；dpph中的o-NO2对二价N的空间屏蔽作用。似乎是该反应熵障碍的主要原因。
• Antioxidation mechanisms of uric acid
  作者：Michael G. Simic、Slobodan V. Jovanovic

  DOI：10.1021/ja00197a042

  日期：1989.7

  One-electron oxidation of uric acid generates the urate radical, which was studied in aqueous solution by pulse radiolysis and oxygen-uptake measurements. Acid-base properties of the uric acid radical were determined, i.e., pKsub a1} = 3.1 plus minus} 0.1 and pKsub a2} = 9.5 plus minus} 0.1. The reaction of the radical with oxygen was too slow to be measured, k < 10sup minus}2} dmsup 3} molsup minus}1}

  尿酸的单电子氧化产生尿酸盐自由基，通过脉冲辐射分解和氧摄取测量在水溶液中进行研究。测定尿酸自由基的酸碱性质，即pKsub a1} = 3.1 plus minus} 0.1 和pK sub a2} = 9.5 plus minus} 0.1。自由基与氧的反应太慢而无法测量，k < 10sup minus}2} dmsup 3} molsup minus}1} ssup minus}1}。单电子氧化还原电位与 NHE 的关系，Esub 7} = 0.59 V，源自氧化还原电位的 pH 依赖性，该电位通过在 pH 7 和 8.9 下测量的值以及先前在 pH 13 下确定的值拟合。尿酸与氧化物质和过氧自由基的快速反应表明尿酸可能是一种水溶性生理抗氧化剂。
• Pedrielli, Pamela; Pedulli, Gian Franco, Gazzetta Chimica Italiana, 1997, vol. 127, # 9, p. 509 - 512
  作者：Pedrielli, Pamela、Pedulli, Gian Franco

  DOI：——

  日期：——