4,4'-dichlorobenzhydrylium ion | 15876-05-8

• 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: 4,4'-dichlorobenzhydrylium ion
• 英文别名: 1-chloro-4-[(4-chlorophenyl)methyl]benzene
• CAS: 15876-05-8
• 化学式: C₁₃H₉Cl₂
• 分子量: 236.12
• InChiKey: XWRHKXWPKUHIFQ-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

• 作为反应物：
  描述：

  4,4'-dichlorobenzhydrylium ion 、 烯丙基三甲基硅烷 在 三氟甲磺酸 、 tetrabutylammonium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 4,4-bis(4-chlorophenyl)-1-butene
  参考文献：
  名称：

  Generation of Diarylcarbenium Ion Pools via Electrochemical C–H Bond Dissociation

  摘要：

  通过二苯甲烷衍生物的低温电化学氧化，生成了二芳基碳正离子"离子池"。除了具有各种取代基的二苯甲烷外，我们还发现9,10-二氢蒽、二苯并苏烯和氧杂蒽等二苯甲烷的稠合衍生物也能作为离子池的前体。通过低温NMR分析和冷喷雾质谱分析证实了二芳基碳正离子的生成。此外，还研究了其与各种碳亲核试剂如烯丙基三甲基硅烷、1,3,5-三甲基苯和茴香的反应活性。

  DOI：

  10.1246/bcsj.82.594
• 作为产物：
  描述：

  [bis(4-chlorophenyl)methyl]triphenylphosphonium tetrafluoroborate 以 水 为溶剂， 生成 4,4'-dichlorobenzhydrylium ion
  参考文献：
  名称：

  六氟异丙醇/水混合物的溶剂亲核性

  摘要：

  捕获在1,1,1,3,3,3-六氟-2-丙醇（HFIP）和水范围从50到99的混合物中捕获的各种供体和受体取代的苯甲基铵离子的一阶速率常数k 1通过在这些溶剂中由苄基三芳基phosph盐进行激光闪光光解生成苄基离子来确定HFIP（w / w）的百分比。从这些速率常数中，我们得出HFIP /水混合物的溶剂特异性反应性参数N 1和s N，由线性自由能关系lg k 1（20°C）=  s N（N 1  +  E）。版权所有©2012 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/poc.3064

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
• Carbocation formation via carbene protonation studied by the technique of stopped-flow laser-flash photolysis
  作者：Simon T. Belt、Cornelia Bohne、G. Charette、S. E. Sugamori、J. C. Scaiano

  DOI：10.1021/ja00059a014

  日期：1993.3

  Photolysis of diaryl diazo compounds in the presence of hydroxylic protonating substrates in acetonitrile leads to the formation of the corresponding carbocations. Quantum yields for these processes have been determined for the first time; for example, photolysis of diphenyldiazomethane in 1:1 acetonitrile/trifluoroethanol produces Ph 2 CH + with a quantum yield of 0.007. The products, formed either

  在乙腈中的羟基质子化底物存在下，二芳基重氮化合物的光解导致形成相应的碳正离子。首次确定了这些过程的量子产率；例如，二苯基重氮甲烷在 1:1 乙腈/三氟乙醇中的光解产生 Ph 2 CH + ，量子产率为 0.007。通过直接插入或通过碳正离子途径形成的产物是相应的醚。动力学分析得出的结论是碳正离子是由单线态卡宾的质子化形成的
• 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.
• Kirmse, Wolfgang; Kilian, Jörg; Steenken, Steen, Journal of the American Chemical Society, 1990, vol. 112, # 17, p. 6399 - 6400
  作者：Kirmse, Wolfgang、Kilian, Jörg、Steenken, Steen

  DOI：——

  日期：——
• 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.