1,1-diphenylethyl radical | 51314-23-9

• 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: 1,1-diphenylethyl radical
• CAS: 51314-23-9
• 化学式: C₁₄H₁₃
• 分子量: 181.257
• InChiKey: HLLHIDGMFDQCJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  1,1-diphenylethyl radical 生成 3,3,4,4-四苯基己烷
  参考文献：
  名称：

  BECKHAUS H.-D.;SCHAETZER J.;RUECHARDT C., TETRAHEDRON LETT., 1983, 24, NO 32, 3307-3310

  摘要：

  DOI：
• 作为产物：
  描述：

  1,1-二苯基乙醇 以 乙腈 为溶剂， 生成 1,1-diphenylethyl radical
  参考文献：
  名称：

  液体中芳甲基自由基的光物理和光化学

  摘要：

  Obtention par radiolyse pulsee des radicaux suivants: benzhydryle et dihydro-10,11 dibenzo(a,d] cycloheptenyle-5 (groupe 1), trityle, α-cyclopropylbenzydryle et diphenyl-1,1ethyle (groupe 2)。 photolyse Laser eclair (λ=347 nm). 荧光练习曲和光反应练习曲. 机制

  DOI：

  10.1021/ja00287a016

文献信息

• Monomer- and polymer radicals of vinyl compounds: EPR and DFT studies of geometric and electronic structures in the adsorbed state
  作者：Anders Lund、Marek Danilczuk

  DOI：10.1016/j.saa.2012.08.054

  日期：2012.12

  paramagnetic resonance (EPR) spectroscopy was applied to study the paramagnetic species formed from styrene, 1,1-diphenylethylene, α-methylstyrene, β-methylstyrene and methylmethacrylate adsorbed on amorphous silica gel after γ-irradiation at 77K. Radicals formed by the hydrogen atom addition at the vinyl group of the monomers were observed in all samples. The hydrogen atoms were shown to originate to

  应用电子顺磁共振（EPR）光谱研究了在77Kγ辐射下吸附在无定形硅胶上的苯乙烯，1,1-二苯基乙烯，α-甲基苯乙烯，β-甲基苯乙烯和甲基丙烯酸甲酯形成的顺磁物质。在所有样品中均观察到通过在单体的乙烯基上加氢原子而形成的自由基。通过使用具有氘代硅烷醇基团的硅胶，显示出氢原子在很大程度上源自吸附剂。对于包含甲基丙烯酸甲酯（MMA）的样品，在升高的温度下观察到分配给自由基的EPR光谱。采用DFT量子化学方法计算了吸附配合物的结构，各自的超细分裂常数和吸附能。对MMA分子与MMA自由基之间的反应以及传播自由基的结构进行了建模。计算出的所有自由基的超细分裂常数证实了实验光谱的归属。
• The reactivity of ketyl and alkyl radicals in reactions with carbonyl compounds
  作者：E. T. Denisov

  DOI：10.1007/bf02494263

  日期：1998.11

  parabolic model of bimolecular radical reactions was used for analysis of the hydrogen transfer reactions of ketyl radicals: >C·OH+R1COR2→>C=O+R1R2C·OH. The parameters describing the reactivity of the reagents were calculated from the experimental data. The parameters that characterize the reactions of ketyl and alkyl radicals as hydrogen donors with olefins and with carbonyl compounds were obtained: >C·OH

  双分子自由基反应的抛物线模型用于分析羰基自由基的氢转移反应：>C·OH+R1COR2→>C=O+R1R2C·OH。描述试剂反应性的参数由实验数据计算。得到表征作为氢供体的羰基和烷基自由基与烯烃和羰基化合物反应的参数：>C·OH+R1CH=CH2→>C=O+R1C·HCH3；>R1CH= +R2C·H R3→R2C·HCH3+R2CH=CHR3。这些参数用于计算这些转换的活化能。比较了自由基和分子（醛、酮和醌）从 C-H 和 O-H 键夺氢反应的动力学参数。
• Twisted molecular geometry and localized electronic structure of the triplet excited gem-diphenyltrimethylenemethane biradical: substituent effects on thermoluminescence and related theoretical calculations
  作者：Yasunori Matsui、Hayato Namai、Ikuko Akimoto、Ken-ichi Kan’no、Kazuhiko Mizuno、Hiroshi Ikeda

  DOI：10.1016/j.tet.2011.06.052

  日期：2011.9

  effects on the energies of electronic transitions (ETs) between the triplet excited and ground states of gem-diphenyltrimethylenemethane biradicals (32a) were explored by using thermoluminescence (TL) spectroscopy and density functional theory (DFT) including time-dependent (TD) DFT. Linear free energy (Hammett) analyses of TL energies of a variety of para-substituted aryl derivatives of 32* gave reasonable

  利用热发光（TL）光谱和密度泛函理论（DFT）包括时间依赖性（TD），探讨了对宝石-二苯基三亚甲基甲烷双自由基（3 2a）的三重激发态和基态之间的电子跃迁（ET）能量的取代基效应。DFT。各种3 2 *的对位取代的芳基衍生物的TL能的线性自由能（Hammett）分析与取代基常数σ具有合理的相关性。数据的Hammett图的斜率几乎与通过对结构相关的1,1-二芳基乙基自由基的光致发光（PL）能量进行的类似分析获得的斜率几乎相同（3*）。结果表明TL 3 2 *和PL 3 *来自共同的二芳基甲基自由基荧光团。DFT和TDDFT计算出的电子结构以及3 2和3的ET能量也支持这种解释。热力学和之间的电荷重组（CR）过程的动力学分析2 +和1 - ，其产生3 2 *，揭示了取代基不仅改变TL能量也的TL强度3 2 *。在此努力中所做的观察表明，3 2 *以及32和2 +具有极大扭曲的分子几何结构和高度局限的电子结构。
• An Evolved Explanation for the Molecular Geometry and Electronic Structure of Diphenyl-Substituted Cyclic Trimethylenemethane in the Ground State:  A Nearly Planar Conformation with a Considerably Localized Electronic State
  作者：Hiroshi Ikeda、Hayato Namai、Hirotsugu Taki、Tsutomu Miyashi

  DOI：10.1021/jo047893o

  日期：2005.5.1

  using 11•• and 13•• support the conclusion based on the experiments and calculations. Therefore, we propose an evolved explanation for the molecular geometry and electronic structure of the ground state of 3•• in a low-temperature matrix, a nearly planar conformation with a considerably localized electronic state, which alone accounts for the spectroscopic characteristics.

  我们重新研究了二苯基取代的五元环状三亚甲基甲烷（TMM）双自由基（Berson's TMM，3 ••）将UV / VIS吸收和发射光谱与密度泛函理论（DFT）和时变（TD）-DFT计算相结合。两个强的吸收带，A和B，与λ AB在298和328纳米，分别，弱吸收带C，与λ AB在472纳米，且强烈的发射带d，与λ EM在491处观察到对3 ••。通过比较3 ••与1,1-二苯乙基（7 •）和环戊-2-烯-1-基（9 •）自由基，发现带B，C和D源自二苯基甲基自由基部分（亚基I），而带A最有可能被分配给与亚基I和残基亚基II之间的相互作用有关的电子跃迁。环戊烯基基团部分。UB3LYP / cc-pVDZ计算表明，在基态下，3 ••尽管它们几乎是平面构型（θ= + 23.5°），但它们主要分别定位在亚基I和II中，它们之间的相互作用效率低下。此外，TD-UB3LYP / cc-pVDZ计算表明吸
• Kinetics of Hydrogen Atom Transfer from (η⁵-C₅H₅)Cr(CO)₃H to Various Olefins:  Influence of Olefin Structure
  作者：Jongwook Choi、Lihao Tang、Jack R. Norton

  DOI：10.1021/ja066325i

  日期：2007.1.1

  Treating (eta(5)-(CH5)-H-5)Cr(CO)(3)H (1) or (eta(5)-C5H5) Cr(CO)(3)D (1-d(1)) with an excess of olefin containing the opposite isotope generally leads to H/D exchange, although hydrogenation is also observed in some cases. Application of an appropriate statistical correction to the observed exchange rate gives k(H) and k(D), the rate constants for H-center dot (D-center dot) transfer from (eta(5)-C5H5) Cr(CO)(3)H (D) to various olefins. The values of k(H) and k(D) vary appreciably with the substituents on the double bond. Phenyl-substituted olefins accept H-center dot more readily than do carbomethoxy-substituted olefins, although the latter accept H-center dot more readily than do alkyl-substituted olefins. A methyl substituent on the incipient radical site increases kH at 323 K by a factor between 5 and 50. A methyl substituent on the carbon to which the H-center dot is being transferred decreases k(H) substantially. On the whole, the rate constants for H-center dot transfer reflect steric effects as well as the stability of the resulting carbon-centered radicals.