di-(p-anisyl)methyl radical | 124605-72-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: di-(p-anisyl)methyl radical
• 英文别名: di(p-methoxyphenyl)methyl radical；An2CH(*)
• CAS: 124605-72-7
• 化学式: C₁₅H₁₅O₂
• 分子量: 227.283
• InChiKey: CWZAQIYYCYXBJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  di-(p-anisyl)methyl radical 以 乙腈 为溶剂， 生成 双(对甲氧基苯基)甲基阳离子
  参考文献：
  名称：

  二（对甲氧基苯基）甲基氯的三色三激光光化学

  摘要：

  使用延迟时间为 100 的 308、355 和 495 nm 激光器通过三步激发研究了二（对甲氧基苯基）甲基氯 ((p-CH3OC6H4)2CHCl = An2CHCl) 的三色三激光光化学纳秒至 3 微秒。二(对甲氧基苯基)甲基自由基 (An2CH•) 与处于激发态的 An2CH• (An2CH•*) 和二(对甲氧基苯基)甲基阳离子 (An2CH+) 一起产生，量子产率为 0.09、0.12 和 0.12，分别是在 308 nm 激光（第一激光）光解 An2CHCl 在乙腈中的激光闪光后。用 355 nm 激光（第二激光）激发 An2CH• 导致形成 An2CH•* 和 An2CH+ 的瞬态吸收和 An2CH•* 的荧光，峰值在 550 nm。从 An2CH• 形成 An2CH+ 需要 355 nm 的双光子能量，并通过 An2CH•* 的顺序激发通过 An2CH• 的共振双光子电离 (RETPI)

  DOI：

  10.1021/jp027002l
• 作为产物：
  描述：

  4,4-二甲氧基二苯基甲烷 在 2,6-二甲基吡啶 作用下， 以 乙腈 为溶剂， 生成 di-(p-anisyl)methyl radical
  参考文献：
  名称：

  Baciocchi; Del Giacco; Elisei, Journal of the American Chemical Society, 1993, vol. 115, # 26, p. 12290 - 12295

  摘要：

  DOI：

文献信息

• Photo-heterolysis and -homolysis of substituted diphenylmethyl halides, acetates, and phenyl ethers in acetonitrile: characterization of diphenylmethyl cations and radicals generated by 248-nm laser flash photolysis
  作者：J. Bartl、S. Steenken、H. Mayr、R. A. McClelland

  DOI：10.1021/ja00175a028

  日期：1990.9

  cations with R = R' = Me to R = H, R' = CF3. The rate constants for reaction of C+ with halides (ion recombination) are -2 X 1O1O M-l s-' (diffusion control). The radicals C' disappear by dimerization and disproportionation, for which a complete mass balance has been achieved by product analysis for the case of the benzhydryl system. At laser-pulse powers > IO mJ electronically excited radicals, C", are

  异裂比均裂吸热小得多。均裂和异裂也可以通过与三线态苯乙酮（由 308 nm 光解产生）的反应间接实现。除非被一种或多种 MeO 稳定，否则阳离子主要通过与乙腈反应生成腈离子而衰变。然而，由于该反应是可逆的（如二苯甲基阳离子所示），腈离子对最终（阳离子衍生）产物的形成贡献很小，这是由与痕量水（主要产物，二苯甲基醇）反应产生的。 ; 次要，二苯甲基乙酰胺）。对于 R = R' = Me 到 R = H，R' = CF3 的阳离子，C+ 加到 CH$N 的速率常数在 3.5 X 105 到 3.8 X IO7 sI 的范围内。C+ 与卤化物（离子复合）反应的速率常数为 -2 X 1O1O Ml s-' （扩散控制）。自由基C'通过二聚和歧化消失，对于二苯甲基体系的情况，通过产物分析已经实现了完全的质量平衡。在激光脉冲功率 > 10 mJ 时，通过基态 C' 吸收光量子，在许多情况下另外形成电子激发自由基
• Dynamics of the transient species generated upon photolysis of diarylmethanes within zeolites — Deprotonation and oxidation reactions
  作者：Suzanne Shea、Norman P Schepp、Amy E Keirstead、Frances L Cozens

  DOI：10.1139/v05-208

  日期：2005.9.1

  The oxidation of diarylmethanes is a multistep process involving initial formation of a radical cation, deprotonation of the radical cation to the radical, and oxidation of the radical to the carbocation. The dynamics and efficiency of the last two steps in this process, namely deprotonation and oxidation, in acidic zeolites and non-acid zeolites are examined in the present work as a function of the acidity of the diarylmethane radical cations and the oxidation potential of the diarylmethyl radicals. Our results indicate that rate constants for deprotonation strongly depend on the acidity of the radical cations, but not on the composition of the zeolites. In addition, oxidation of the radicals to the diarylmethyl cations is strongly dependent on both the oxidation potential of the radicals and the oxidizing ability of the zeolite. This dependence allows oxidation potentials of the zeolites to be estimated.Key words: radical cations, carbocations, zeolites, laser flash photolysis.

  二苯甲烷的氧化是一个多步过程，涉及到首先形成自由基阳离子，自由基阳离子去质子化成自由基，以及将自由基氧化成碳阳离子。本文研究了这个过程中最后两个步骤，即去质子化和氧化在酸性沸石和非酸性沸石中的动态和效率，这取决于二苯甲烷自由基阳离子的酸度和二苯甲基自由基的氧化电位。我们的结果表明，去质子化的速率常数强烈依赖于自由基阳离子的酸度，但不依赖于沸石的组成。此外，将自由基氧化为二苯甲基阳离子强烈依赖于自由基的氧化电位和沸石的氧化能力。这种依赖关系可以估算沸石的氧化电位。关键词：自由基阳离子、碳阳离子、沸石、激光闪光光解。
• Photoionization of diarylmethyl radicals in acetonitrile and alcohol-water: laser flash production of diarylcarbenium ions
  作者：Joaquim L. Faria、S. Steenken

  DOI：10.1021/j100111a034

  日期：1993.3

  Diarylmethyl radicals Ar2CH. were produced by 248-nm laser photolysis (20 ns) of diphenylmethane, diphenylmethanol, and diarylmethyl halides in acetonitrile and water:alcohol mixtures. A few microseconds after their generation, the radicals were subjected to a laser pulse (20 ns) of 308-nm light. As products of the photolysis of the radicals, the electronically excited radicals, Ar2CH.* (D] state), and the corresponding cations, Ar2CH+, were identified. The electronically excited radicals decay with emission of light (almost-equal-to 550 nm in the case of Ph2CH.*) to their ground state (D0), whereas the cations react with solvent or (other) nucleophiles. The formation of cation from AT2CH. requires two photons (is biphotonic) and proceeds by photoionization of Ar2CH.*. The photoejected electrons were directly observed in aqueous alcohol. In acetonitrile, the yield of photoionization of Ar2CH. (as measured greater-than-or-equal-to 20 ns after the 308-nm pulse) can be increased by the electron scavenger n-butyl chloride, which does not react with Ar2CH.*. In contrast, CCl4, which does react with Ar2CH.*, does not lead to an increase in cation yield.
• Picosecond Kinetic Study of the Dynamics for Photoinduced Homolysis and Heterolysis in Diphenylmethyl Chloride
  作者：Matthew Lipson、Ashok A. Deniz、Kevin S. Peters

  DOI：10.1021/jp952672v

  日期：1996.1.1

  The kinetics of both the ions and radicals formed upon photolysis of diphenylmethyl chloride, (4-methoxyphenyl )phenylmethyl chloride, and bis(4-methoxyphenyl) methyl chloride in acetonitrile and propionitrile are examined by picosecond pump-probe spectroscopy. Both radical pairs and ion pairs are formed directly from a common excited state. In addition, the geminate radical pair decays by electron transfer to form either the contact ion pair or a covalent bond, as well as undergoes diffusional separation to free radicals.
• Protonation of Diarylcarbenes by Alcohols: The Importance of Ion Pair Dynamics
  作者：Edward J. Dix、Joshua L. Goodman

  DOI：10.1021/j100099a025

  日期：1994.12

  Picosecond laser excitation of either di(p-chlorophenyl)- or di(p-methoxyphenyl)diazomethane generates a transient which we ascribe to the singlet states of di(p-chlorophenyl)- and di(p-methoxyphenyl)carbenes, 1a and 1b, respectively. Picosecond absorption spectroscopy is used to determine their kinetic behavior in various solvents. In the presence of alcohols, these carbenes are protonated, forming contact-ion pairs. These ion pairs partition between collapse to ether products and separation to free carbeneium ions, 2a and 2b, which are readily observed. The dynamics of these ion pairs is discussed. Protonation of carbenes can provide an alternative method for the preparation of ion pairs and the investigation of their dynamics.