p,p'-Dichlorodiphenylmethyl radical | 28760-96-5

• 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: p,p'-Dichlorodiphenylmethyl radical
• CAS: 28760-96-5
• 化学式: C₁₃H₉Cl₂
• 分子量: 236.12
• InChiKey: UJHPCKUVCNIHEK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  p,p'-dichlorodiphenylmethylene 在 2,2,2-三氟乙醇 作用下， 以 乙腈 为溶剂， 生成 p,p'-Dichlorodiphenylmethyl radical
  参考文献：
  名称：

  Protonation of Diarylcarbenes by Alcohols: The Importance of Ion Pair Dynamics

  摘要：

  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.

  DOI：

  10.1021/j100099a025

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
• Photolytic Generation of Benzhydryl Cations and Radicals from Quaternary Phosphonium Salts: How Highly Reactive Carbocations Survive Their First Nanoseconds
  作者：Johannes Ammer、Christian F. Sailer、Eberhard Riedle、Herbert Mayr

  DOI：10.1021/ja3017522

  日期：2012.7.18

  concentrations in CH(3)CN, the precursor salts are mostly unpaired, and the photo-cleavage mechanism is independent of the nature of the counter-anions. Dichloromethane is better suited for generating the more reactive benzhydryl cations than the more polar and more nucleophilic solvents CH(3)CN or CF(3)CH(2)OH. Efficient photo-generation of the most reactive benzhydryl cations (3,5-F(2)-C(6)H(3))(2)CH(+)

  二苯甲基三芳基鏻盐 Ar(2)CH-PAr(3)(+)X(-) 的 UV 照射（266 或 280 nm）产生二苯甲基阳离子 Ar(2)CH(+) 和/或二苯甲基自由基 Ar(2)CH (•)。通过纳秒激光闪光光解和使用最先进的飞秒瞬态光谱仪的超快光谱研究了光裂解的效率和机制。光电离剂 (Ar(2)CH(+))、光电离核器 (PPh(3) 或 P(p-Cl-C(6)H(4))(3))、反离子的影响(X(-) = BF(4)(-)、SbF(6)(-)、Cl(-) 或 Br(-))，以及溶剂 (CH(2)Cl(2) 或 CH(3) )CN) 进行了调查。从 Ar(2)CH-PAr(3)(+)BF(4)(-) 或 -SbF(6)(-) 光生碳正离子比从典型的中性前体（例如二苯甲基氯或溴化物）更有效. 鏻盐的光化学由离子配对程度控制，这取决于溶剂和鏻盐的浓度。通过光解具有复合抗衡离子（X(-) =
• Photohomolysis and Photoionization of Substituted Tetraphenylethanes and C-C Fragmentation of 1,1,2,2-Tetra(p-R-phenyl)ethane Radical Cations (R=H, CH3, OCH3, Cl)
  作者：Joaquim L. Faria、Robert A. McClelland、Steen Steenken

  DOI：10.1002/(sici)1521-3765(19980710)4:7<1275::aid-chem1275>3.0.co;2-x

  日期：1998.7.10

  On photolysis of a series of tetraphenylethanes in 2,2,2-trifluoroethanol (TFE) solution with 248 nm light, homolysis of the central C-C bond occurs to yield the corresponding substituted diphenylmethyl radicals, in a process requiring one quantum of light. A second process takes place under conditions of high photon fluxes, namely biphotonic photoionization to produce a radical cation, which subsequently undergoes efficient C-C scission of the aliphatic central bond to yield the radical and carbocation fragments. Photoionization and photohomolysis are the preferred processes of excited state deactivation in the solvents acetonitrile, TFE, and 1,1,1,3,3,3-hexafluoroisopropanol. The lifetime of the radical cation could be directly determined by following the formation rates of the fragments in solution. The cations were characterized by their UV absorption spectra and electrophilic reactivities.
• 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.
• 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.