苯基过氧自由基 | 91422-02-5

• 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: 苯基过氧自由基
• 英文名称: phenyl peroxy radical
• CAS: 91422-02-5
• 化学式: C₆H₅O₂
• 分子量: 109.105
• InChiKey: VRICPVXYTCCWOE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 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：
  10.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  苯基过氧自由基 在 air 、 Fe(CN)6 作用下， 以 various solvent(s) 为溶剂， 生成 Oxidooxybenzene
  参考文献：
  名称：

  亚铁和亚铁氰化物离子被过氧自由基氧化

  摘要：

  在水溶液中通过脉冲辐射分解产生烷基过氧自由基和芳基过氧自由基，并通过动力学分光光度法研究它们与亚铁和亚铁氰化物离子的反应。Fe（CN）6 4-的氧化速率常数从<1×10 5到5×10 7 L mol -1 s -1变化，这取决于取代基对过氧自由基和电子的吸电子作用。大概反映了过氧自由基还原电位的变化，这是外球电子转移所期望的。Fe aq 2+的氧化另一方面，是通过受水配体的解离交换速率控制的内球机理发生的。所述速率常数分别为几乎相同的所有过氧自由基检查（ķ =（0.5-1.1）×10 6大号摩尔-1小号-1）和所涉及的瞬时中间体的形成，RO 2 -的Fe 3+，后来分解产生Fe aq 3+。H +和Fe 2+促进分解。所提出的机理是对先前提出的反应方案的修改。

  DOI：

  10.1021/jp9533335
• 作为产物：
  描述：

  环己三烯 在 氧气 作用下， 以 gas 为溶剂， 24.9~133.9 ℃ 、5.0 kPa 条件下， 生成 苯基过氧自由基
  参考文献：
  名称：

  A cw Laser Absorption Study of the Reactions of Phenyl Radicals with NO, NO2, O2 and Selected Organics Between 298-404 K

  摘要：

  AbstractRate constant for the reactions of phenyl (C6H5) radicals with NO, NO2, O2, C2H4, 2‐butene, benzene, toluene and CCl4 have been determined using a combined laser photolysis/laser absorption technique. Phenyl radicals were generated by 248 nm excimer laser photolysis of C6H5X, where X = Cl, Br and NO. Their temporal behaviour was monitored using cw‐laser line absorption in the X̃2A1‐Ã2B1 transition at 488 nm. At this wavelength the absorption cross section of phenyl has been determined as (9 ± 4) 10−19 cm2. For the rate coefficients of reaction with (1) NO, (2) NO2 and (3) O2 in the temperature range 298‐404 K the following expressions were obtained. magnified image The magnitude of the rate coefficients k1 and k2 and their negative temperature dependence suggest that the reactions between phenyl and NO/NO2 occur as radical recombination and/or (in the case of NO2) as O‐atom metathesis reaction. The apparent low reactivity of phenyl with O2 is likely to be caused by insufficient thermal stability of the phenylperoxy radical. For the reactions of phenyl with selected organics the following upper limits of the rate coefficient at 298 K were determined: k4 (C2H4) ≤ 8 · 10−17 cm3/s; k5 (C2H2) ≤ 8 · 10−16 cm3/s; k6 (2‐butene) ≤ 8 · 10−17 cm3/s; k7 (benzene) ≤ 3 · 10−15 cm3/s; k8 (toluene) ≤ 2 · 10−14 cm3/s and k9 (CCl4) ≤ 1 · 10−15 cm3/s. These limits did not change significantly even around 400 K.

  DOI：

  10.1002/bbpc.19890931205

文献信息

• Matrix Isolation and IR Characterization of the Benzoyl and Benzoylperoxy Radicals
  作者：Artur Mardyukov、Wolfram Sander

  DOI：10.1002/ejoc.201000153

  日期：2010.5

  The benzoyl radical 1 was synthesized in argon matrices by the thermal reaction of the phenyl radical 2 with CO. The IR spectrum with the C=O str. vibration at 1824.4 cm–1 is in good agreement with DFT calculations. The formation of 1 is reversible and UV irradiation results in the cleavage back to 2 and CO. The benzoyl radical 1 can react with molecular oxygen in the matrix to produce the benzoylperoxy

  通过苯基自由基 2 与 CO 的热反应，在氩气基质中合成了苯甲酰基自由基 1。C=O str 的红外光谱。1824.4 cm-1 处的振动与 DFT 计算非常吻合。1 的形成是可逆的，紫外线照射导致裂解回 2 和 CO。苯甲酰自由基 1 可以与基质中的分子氧反应生成苯甲酰过氧自由基 3。自由基 3 还通过红外光谱结合 DFT 进行表征计算。
• Matrix Isolation and Spectroscopic Characterization of the Phenylperoxy Radical and Its Rearranged Products
  作者：Artur Mardyukov、Wolfram Sander

  DOI：10.1002/chem.200801546

  日期：2009.1.26

  [H5]‐18O2‐1, and [D5]‐18O2‐1 were matrix‐isolated and characterized by IR spectroscopy. The experimental IR spectra are in excellent agreement with results from DFT calculations. Irradiation of 1 with visible light produces the 2‐oxepinoxy radical 5 in a clean reaction. Subsequent irradiation results in ring‐opening and formation of several conformers of ketoketene 6. The radicals 1, 5, and 6 play an important

  所述phenylperoxy自由基1已被苯基基团的反应，合成2与3 ö 2。自由基1可以在气相中生成，然后在10 K下捕获在固态氩中，也可以在氩气基质中直接合成。通过使2以及它的氘化同位素[d 5 ] - 2与16 ö 2，并用18 ö 2分别四个同位素[H 5 ] - 16 ø 2 - 1 [d 5 ] - 16O 2 ‐ 1，[H 5 ] ‐ 18 O 2 ‐ 1和[D 5 ] ‐ 18 O 2 ‐ 1进行了基质分离，并通过红外光谱进行了表征。实验的红外光谱与DFT计算的结果非常吻合。用可见光照射1可以在干净的反应中产生2-氧杂氧自由基5。随后的辐照导致开环并形成了多个酮基烯6构象异构体。基团1，5，和6 在芳烃的燃烧中起着重要作用，现在可以首次进行分离和光谱表征。
• Mertens, Ralf; Sonntag, Clemens von, Angewandte Chemie, 1994, vol. 106, # 12, p. 1323 - 1326
  作者：Mertens, Ralf、Sonntag, Clemens von

  DOI：——

  日期：——
• Rate of reaction of phenyl radicals with oxygen in solution and in the gas phase
  作者：Paul M. Sommeling、Peter Mulder、Robert Louw、David V. Avila、Janusz Lusztyk、K. U. Ingold

  DOI：10.1021/j100134a001

  日期：1993.8

  The rate constant for the title reaction, k1, is 3.8 X 10(9) M-1 s-1 in water at 298 K and is greater-than-or-equal-to 10(8) M-1 s-1 in the gas phase at 603 K. It is concluded that two reports8,11 that this reaction is very slow in the gas phase, k1 less-than-or-equal-to 1.2 X 10(4) and approximately 2.3 X 10(6) M-1 s-1, are in error.
• Formation and Reactions of Halogenated Phenylperoxyl Radicals in Aqueous Alcohol Solutions
  作者：G. I. Khaikin、Z. B. Alfassi、P. Neta

  DOI：10.1021/j100029a023

  日期：1995.7

  Halogenated phenylperoxyl radicals were produced in irradiated aqueous alcohol solutions by reductive dehalogenation of dihalo- and polyhalobenzenes with solvated electrons and subsequent reaction of the halophenyl radicals with oxygen. Phenylperoxyl radicals oxidize 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate ion) (ABTS(2-)) with rate constants between 3 x 10(7) and 3 x 10(9) L mol(-1) s(-1), depending on the structure of the peroxyl radical and the alcohol concentration. For monohalogenated phenylperoxyl radicals, the reactivity changed in the order F < Cl < Br and p < m < o. The reactivity increased on going from the (monohalophenyl)- to the (dihalophenyl)- and (trihalophenyl)peroxyl radicals. The rate constants were correlated with the substituent constants and with the pK(a) values of similarly halogenated phenols. The reduction potential for PhOO(.)/PhOO(-) was estimated to be near 0.7 V vs NHE; that for the trichloro derivative, near 0.9 V. The rate constants in various solvent mixtures were correlated with the cohesive pressure of the medium.