Peroxidradikal v. Diphenylmethan | 20387-24-0

• 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: Peroxidradikal v. Diphenylmethan
• CAS: 20387-24-0
• 化学式: C₁₃H₁₁O₂
• 分子量: 199.229
• InChiKey: IIRFHFKEHOSOSQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.14
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  29.13
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  Peroxidradikal v. Diphenylmethan 在 偶氮二异丁腈 、 (E)-3-(3,4-dihydroxyphenyl)-1-phenylprop-2-en-1-one 、 氧气 作用下， 以 二甲基亚砜 、 氯苯 为溶剂， 生成 diphenylmethyl hydroperoxide
  参考文献：
  名称：

  Antioxidant activity of chalcones: The chemiluminescence determination of the reactivity and the quantum chemical calculation of the energies and structures of reagents and intermediates

  摘要：

  Six antioxidants from the class of chalcones (ArOH), compounds from which flavonoids are obtained in nature, were studied. The antiradical activity of chalcones and a number of related compounds was determined by a chemiluminescence method using the scavenging of peroxide radicals ROO(center dot) + ArOH -> ROOH + OAr(center dot) (with the rate constant k (7)) in a model reaction of diphenylmethane (RH) oxidation. The structures and energies of the reagents and intermediates were determined by semiempirical quantum chemical (PM3, PM6) calculations. 3,4-Dihydroxychalcone and caffeic acid, which have a catechol structure, that is, two neighboring OH groups in phenyl ring B, exhibited high antioxidant activity (k (7) a parts per thousand 10(7) l mol(-1) s(-1)); this is consistent with the lowest bond strengths D(ArO-H) of 79.2 and 76.6 kcal/mol, respectively. The abstraction of a hydrogen atom by the ROO(center dot) radical is the main reaction path of these compounds; however, the low stoichiometric coefficients of inhibition (f = 0.3-0.7) suggest a contribution of secondary and/or side reactions of ArOH and OAr(center dot). In the other chalcones, the ArO-H bond is stronger (D(ArO-H) = 83-88 kcal/mol) and the antioxidant activity is lower (k (7) = 10(4)-10(5) l mol(-1) s(-1)).

  DOI：

  10.1134/s0023158410040087
• 作为产物：
  描述：

  benzhydryl(phenyl)sulfane 以 乙腈 为溶剂， 生成 Peroxidradikal v. Diphenylmethan
  参考文献：
  名称：

  以氧和硫为中心的自由基对单线态氧的淬灭：能量转移到溶液中过氧自由基的证据

  摘要：

  在液体溶液中研究了 PhS•、PhSO• 和过氧自由基 PhOO•、t-BuOO•、PhCH2OO•、Ph2CHOO• 和 Ph3COO• 对 1.27 μm 单线态氧发光的淬灭。通过使用纳秒瞬态吸收测量导致自由基形成的不同引发剂分解的量子产率。这允许通过自由基确定单线态氧 O2(1Δg) 淬灭速率常数。对于以硫为中心的自由基，它们是 <2 × 108 M-1 s-1，对于乙腈中的过氧自由基，它们是 (2−7) × 109 M-1 s-1。快速淬灭归因于过氧化物的能量转移淬灭，其具有 n → π* 跃迁，导致其 2A'' 基态上方的低位 2A' 状态。PhSO• 在计算上显示不具有如此低的 2A' 状态。可能有一个非常低的 2B1 状态，对于 PhS•，

  DOI：

  10.1021/ja9730831

文献信息

• Free electron transfer mirrors rotational conformers of substituted aromatics: Reaction of benzyltrimethylsilanes with n-butyl chloride parent radical cations
  作者：Ortwin Brede、Ralf Hermann、Sergej Naumov、Antonios K. Zarkadis、Gerasimos P. Perdikomatis、Michael G. Siskos

  DOI：10.1039/b402052a

  日期：——

  chloride parent radical cations, the singlet ground state conformers are converted into two kinds of radical cations. The cations tending to the planar type are stable whereas those of the twisted type dissociate immediately into benzyl type radicals (p-R3–C6H4–C˙R1R2) and trimethylsilyl cations. The above mentioned product pattern and quantum-chemical calculations on characteristic parameters of the ground

  芳环的较大取代基的旋转运动伴随着最高占据分子轨道的电子密度波动。对于苄基三甲基硅烷 p-R3–C6H4––CR1R2(SiMe3) [R3 = H,PhCO; R1, R2 = H,H; H,我; 我，我；H,Ph; Ph,Ph] 含甲硅烷基的取代基在芳族部分和苄基碳之间的轴上旋转，如式中所示。在此轮换过程中，通过了各种构象异构体。为简单起见，我们将这种多样性简化为两种（极端）边界结构，一种是取代基与芳环在同一平面内（瞬态），另一种是取代基扭曲 90°（稳定结构）。在从构象异构体混合物到正丁基氯母体自由基阳离子的非常快速且不受阻碍的电子转移中，单线态基态构象异构体被转化为两种自由基阳离子。倾向于平面型的阳离子是稳定的，而扭曲型的阳离子则立即解离成苄基型自由基（p-R3- -C˙R1R2）和三甲基甲硅烷基阳离子。上述关于基态构象异构体和产物阳离子的特征参数的产物模式和量子化学计算表明，
• Rate constants for reduction of substituted methylperoxyl radicals by ascorbate ions and N,N,N',N'-tetramethyl-p-phenylenediamine
  作者：P. Neta、R. E. Huie、S. Mosseri、L. V. Shastri、J. P. Mittal、P. Maruthamuthu、S. Steenken

  DOI：10.1021/j100347a045

  日期：1989.5