o-xylyl radical | 2348-48-3

• 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: o-xylyl radical
• 英文别名: o-methylbenzyl radical；o-Xylyl-Radikal；2-methylbenzyl radical
• CAS: 2348-48-3
• 化学式: C₈H₉
• 分子量: 105.159
• InChiKey: DTBHRRDGLARWLZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1-(碘甲基)-2-甲基苯 生成 o-xylyl radical
  参考文献：
  名称：

  Free Radicals by Mass Spectrometry. VIII. The Ionization Potentials ofPara‐, Ortho‐,andMeta‐Xylyl Radicals

  摘要：

  The vertical ionization potentials of the para-, ortho- and meta-xylyl radicals as measured by electron impact are found to be 7.46±0.03, 7.61±0.05, and 7.65±0.03 v, respectively. The thermal dissociation of the para- and ortho-xylyl radicals to form the quinodimethanes has been observed. The meta-xylyl radical was found to have a considerably greater thermal stability.

  DOI：

  10.1063/1.1700853

文献信息

• Photo- and radiation-chemical production of radical cations of methylbenzenes and benzyl alcohols and their reactivity in aqueous solution
  作者：Claudia Russo-Caia、Steen Steenken

  DOI：10.1039/b109974d

  日期：2002.4.4

  Radical cations of methylated benzenes and benzyl alcohols were generated by photoionization and by reaction with the oxidant SO4˙− in aqueous solution. The photoionization requires two 248 nm photons. The lifetimes and absorption spectra of the radical cations produced were determined by time-resolved conductance and optical detection, and the reaction products were measured by GC. As expected, the

  甲基化苯和苯甲醇的自由基阳离子是通过光电离和在水溶液中与氧化剂 SO4˙− 反应生成的。光电离需要两个 248 nm 光子。通过时间分辨电导和光学检测确定产生的自由基阳离子的寿命和吸收光谱，并通过GC测量反应产物。正如预期的那样，自由基阳离子寿命随着额外甲基数量的增加而强烈增加，甲基或羟甲基的去质子化与（水）添加到环位置的比率也是如此。在甲苯的情况下，自由基阳离子的化学寿命 τ 似乎为 10–100 ps ≤ τ ≤ 20 ns，即比离子对分离成游离（溶剂化）离子所需的时间更长，它主要通过向环上加水而不是通过甲基去质子化来反应。进一步的观察是，与甲氧基化类似物相比，甲基化苯甲醇自由基阳离子更具反应性，因此不需要甲氧基化苯甲醇型自由基阳离子通常需要的 OH- 诱导侧链断裂.
• Kinetic Study of the Phthalimide <i>N</i>-Oxyl Radical in Acetic Acid. Hydrogen Abstraction from Substituted Toluenes, Benzaldehydes, and Benzyl Alcohols
  作者：Nobuyoshi Koshino、Basudeb Saha、James H. Espenson

  DOI：10.1021/jo0348017

  日期：2003.11.1

  N-oxyl (PINO) radical was generated by the oxidation of N-hydroxyphthalimide (NHPI) with Pb(OAc)4 in acetic acid. The molar absorptivity of PINO* is 1.36 x 10(3) L mol(-1) cm(-1) at lambda(max) 382 nm. The PINO radical decomposes slowly with a second-order rate constant of 0.6 +/- 0.1 L mol(-1) s(-1) at 25 degrees C. The reactions of PINO(*) with substituted toluenes, benzaldehydes, and benzyl alcohols

  邻苯二甲酰亚胺N-氧基（PINO）自由基是通过在乙酸中用Pb（OAc）4氧化N-羟基邻苯二甲酰亚胺（NHPI）生成的。PINO *在λ（最大）382 nm处的摩尔吸收率为1.36 x 10（3）L mol（-1）cm（-1）。PINO自由基在25摄氏度下以0.6 +/- 0.1 L mol（-1）s（-1）的二级速率常数缓慢分解。PINO（*）与取代的甲苯，苯甲醛和苄醇的反应在氩气气氛下进行了研究。通过Hammett分析将二阶速率常数关联起来。与甲苯和苄醇的反应与sigma +的相关性更好（rho = -1.3和-0.41），与苯甲醛的反应与sigma +的相关性更好（rho = -0.91）。还研究了动力学同位素效应，并获得了相当大的k（H）/ k（D）值：25.0（对二甲苯），27。在25摄氏度下为1（甲苯），27.5（苯甲醛）和16.9（苄醇）。从与对二甲苯和对二甲苯-d（10​​）
• Pyrolysis of alkyl benzenes. Relative stabilities of methyl-substituted benzyl radicals
  作者：Barrie D. Barton、Stephen E. Stein

  DOI：10.1021/j100454a007

  日期：1980.8
• One-electron oxidation of alkylbenzenes in acetonitrile by photochemically produced nitrate radical: evidence for an inner-sphere mechanism
  作者：Tiziana Del Giacco、Enrico Baciocchi、Steen Steenken

  DOI：10.1021/j100123a003

  日期：1993.5

  The reaction between NO3. and polyalkylbenzenes was studied using 308-nm laser flash photolysis of cerium(IV) ammonium nitrate in the presence of the alkylbenzenes in acetonitrile solution. For all benzenes, with the exception of monoalkylbenzenes and o- and m-xylene, the reaction with NO3. was found to yield the corresponding radical cations and to proceed in an apparently straightforward bimolecular manner. For monoalkylbenzenes and o- and m-xylene, radicals were seen which are derived from the parents by formal loss of H. from the side chain of the aromatic. This reaction proceeds via a complex between the aromatic and NO3. with the decomposition of the complex being rate determining at higher concentrations of aromatic (rate constants for decomposition between 6 x 10(5) and 4 x 10(7) s-1). In the complex, electron transfer from the aromatic to NO3. is suggested to be concerted with deprotonation of the incipient radical cation. Formation of a complex between NO3. and aromatic is likely even in those cases where radical cations are observed, with the assumption that in these cases the complex decomposition rate is greater-than-or-equal-to 6 x 10(7) s-1.
• Primary photochemical processes in aromatic molecules. Part 4.—Side-chain photolysis in rigid media
  作者：G. Porter、E. Strachan

  DOI：10.1039/tf9585401595

  日期：——