2-苯基异丙基自由基 | 4794-07-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-苯基异丙基自由基
• 英文名称: 2-phenylisopropyl radical
• 英文别名: cumyl radical；2-Phenyl-2-propyl radical
• CAS: 4794-07-4
• 化学式: C₉H₁₁
• 分子量: 119.186
• InChiKey: MIWQHLIBMIMIRX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  2-苯基异丙基自由基 以 various solvent(s) 为溶剂， 生成 2,3-二甲基-2,3-二苯基丁烷
  参考文献：
  名称：

  Entropy Control of the Cross-Reaction between Carbon-Centered and Nitroxide Radicals

  摘要：

  Absolute rate constants for the cross-coupling reaction of several carbon-centered radicals with various nitroxides and their temperature dependence have been determined in liquids by kinetic absorption spectroscopy. The rate constants range from <2 x 10(5) M-1 s(-1) to 2.3 x 10(9) M-1 s(-1) and depend strongly on the structure of the nitroxide and the carbon-centered radical. Grossly, they decrease with increasing rate constant of the cleavage of the corresponding alkoxyamine. In many cases, the temperature dependence shows a non-Arrhenius behavior. A model assuming a short-lived intermediate that is hindered to form the coupling product by an unfavorable activation entropy leads to a satisfactory analytic description. However, the behavior is more likely due to a barrierless single-step reaction with a low exothermicity where the free energy of activation is dominated by a large negative entropy term.

  DOI：

  10.1021/ja0036460
• 作为产物：
  描述：

  trans azocumene 以 环己烷 为溶剂， 20.0 ℃ 、1.33 Pa 条件下， 生成 2-苯基异丙基自由基
  参考文献：
  名称：

  通过吸收光谱法和DFT计算获得的1,4-二苯基环己烷-1,4-二基自由基阳离子中存在明显的贯通空间和贯通键电子耦合的证据。

  摘要：

  N-甲基喹啉四氟硼酸酯/联苯的光敏单电子转移促进了2,5-二苯基-1,5-己二烯的氧化，在476 nm处形成强烈的电子吸收带，这是由于1,4-二苯基环己烷-1,4-二基自由基阳离子。此瞬态的最大吸收值（λ（ob））发生在比对枯基自由基或对枯基阳离子组分预期的更长的波长处。CH（3）O，CH（3），F，Cl和Br取代该自由基阳离子中苯基的对位会导致lambda（ob）的红移越来越大。比较Rho值，该值是从自由基阳离子相对于sigma（+）的电子跃迁能的Hammett图获得的，与对枯基阳离子的对数的关系表明，取代基对1，4-二芳基环己烷-1，4-二基自由基阳离子的跃迁能的影响约占对对枯基阳离子跃迁能的影响的一半。观察到的取代基引起的lambda（ob）的红移和lambda（ob）对取代基变化的降低的敏感性是根据以下建议：在异丙基的枯基和枯基阳离子部分之间存在明显的贯穿空间和-键电子相互作用。 1

  DOI：

  10.1002/chem.200700820

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 Role of Structural Effects on the Reactions of Alkoxyl Radicals with Trialkyl and Triaryl Phosphites. A Time-Resolved Kinetic Study
  作者：Massimo Bietti、Alessandra Calcagni、Michela Salamone

  DOI：10.1021/jo100703b

  日期：2010.7.2

  kinetic study on the reactions of alkoxyl radicals with trialkyl and triaryl phosphites ((RO)3P: R = Me, Et, i-Pr, t-Bu; (ArO)3P: Ar = C6H5, 2,4-(t-Bu)2C6H3) has been carried out. In the (RO)3P series, the alkoxyl radicals (cumyloxyl (CumO•) and benzyloxyl (BnO•)) undergo addition to the phosphorus center with formation of intermediate tetraalkoxyphosphoranyl radicals (R′OP•(OR)3: R = Me, Et, i-Pr, t-Bu;

  烷氧基与亚磷酸三烷基酯和亚磷酸三芳基酯（（RO）3 P：R = Me，Et，i -Pr，t -Bu;（ArO）3 P：Ar = C 6 H 5，已经进行了2，4-（t- Bu）2 C 6 H 3）。在（RO）3 P系列中，烷氧基（枯基氧基（CumO •）和苄氧基（BnO •））加入磷中心，形成中间四烷氧基磷杂烷基（R'OP •（OR）3：R = Me ，等等，i -Pr，t -Bu; R'= Bn，总和）。添加速率常数受空间效应的影响，从R = Me到R = t -Bu以及从BnO •到CumO •降低。还确定了磷烷基基团R'OP •（OR）3的β断裂速率常数，对于给定的烷基R，按下列顺序增加：R'=叔丁基
• Lifetimes and UV-visible absorption spectra of benzyl, phenethyl, and cumyl carbocations and corresponding vinyl cations. A laser flash photolysis study
  作者：Frances L Cozens、V M Kanagasabapathy、Robert A McClelland、Steen Steenken

  DOI：10.1139/v99-210

  日期：1999.12.5

  Benzyl (4-MeO, 4-Me, and 4-methoxy-1-naphthylmethyl), phenethyl (4-Me₂N, 4-MeO, 3,4-(MeO)₂, 4-Me, 3-Me, 4-F, 3-MeO, 2,6-Me₂, parent, and 4-methoxy-1-naphthylethyl) and cumyl (4-Me₂N, 4-MeO, 4-Me, parent) cations have been studied by laser flash photolysis (LFP) in 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). In most cases styrene or α-methylstyrene precursors were employed for the phenethyl and cumyl ions, the intermediate being obtained by solvent protonation of the excited state. Benzyl cations were generated by photoheterolysis of trimethylammonium and chloride precursors. While a 4-MeO substituent provides sufficient stabilization to permit observation of cations in TFE, cations with less stabilizing substituents usually require the less nucleophilic HFIP. Even in this solvent, the parent benzyl cation is too short-lived (lifetime <20 ns) to be observed. When generated in HFIP, phenethyl cations can be seen to react with unphotolyzed styrene, giving rise to dimer cations that are observed to grow in as the initial phenethyl cation decays. The dimer cations, in common with the oligomer cations seen in cationic styrene polymerization, have a λ_max 15-20 nm higher than the monomer and react with both solvent and styrene several orders of magnitude more slowly. This stabilization relative to the phenethyl may reflect an interaction with the aryl group present at the gamma-carbon. Cations 4-MeOC₆H₄C⁺(R)-CH₃ (R = Me, Et, i-Pr, t-Bu, cyclopropyl, C₆H₅, 4-MeOC₆H₄) were generated in TFE via the photoprotonation route. The alkyl series shows that steric effects are important in the decay reaction. The cation with R = cyclopropyl is a factor of 1.5 less reactive than the cation where R = phenyl. Several vinyl cations have also been generated by photoprotonation of phenylacetylenes. ArC⁺=CH₂ has a reactivity very similar to that of its analog ArC⁺H-CH₃, the vinyl cation being slightly (factors of 2-5) shorter-lived. For the various series of cations, including vinyl, substituents in the aryl ring have a consistent effect on the λ_max, a shift to higher wavelength relative to hydrogen of 15 nm for 4-Me, 30 nm for 4-MeO, and 50 nm for 4-Me₂N.Key words: photogenerated carbocations, carbocation lifetime, styrene, photoprotonation.

  苯甲基（4-MeO，4-Me和4-甲氧基-1-萘基甲基）、苯乙基（4-Me2N，4-MeO，3,4-(MeO)2，4-Me，3-Me，4-F，3-MeO，2,6-Me2，母体和4-甲氧基-1-萘基乙基）和叔丁基（4-Me2N，4-MeO，4-Me，母体）阳离子在2,2,2-三氟乙醇（TFE）和1,1,1,3,3,3-六氟异丙醇（HFIP）中通过激光闪光光解（LFP）进行了研究。在大多数情况下，苯乙烯或α-甲基苯乙烯前体被用于苯乙基和叔丁基离子，中间体通过溶剂质子化激发态而获得。苯甲基阳离子是通过三甲基铵和氯化物前体的光异裂生成的。虽然4-MeO取代基提供了足够的稳定性以在TFE中观察到阳离子，但具有较少稳定取代基的阳离子通常需要较不亲核的HFIP。即使在这种溶剂中，母体苯甲基阳离子也太短寿命（寿命<20 ns）而无法观察到。在HFIP中生成的苯乙基阳离子可以看到与未经光解的苯乙烯反应，导致观察到的二聚体阳离子在初始苯乙基阳离子衰减时增长。与阳离子苯乙烯聚合中观察到的寡聚体阳离子一样，二聚体阳离子的λmax比单体高15-20 nm，并且与溶剂和苯乙烯反应速度慢几个数量级。相对于苯乙基的这种稳定性可能反映了与伽马碳上存在的芳基的相互作用。在TFE中通过光质子化途径生成了4-MeOC6H4C+(R)-CH3（R = Me，Et，i-Pr，t-Bu，环丙基，C6H5，4-MeOC6H4）阳离子。烷基系列表明立体效应在衰减反应中很重要。当R = 环丙基时，其反应性比R = 苯基的阳离子少1.5倍。还通过对苯乙炔的光质子化生成了几种乙烯阳离子。ArC+=CH2的反应性与其类似物ArC+H-CH3非常相似，乙烯阳离子寿命略短（2-5倍因子）。对于包括乙烯在内的各系列阳离子，芳香环中的取代基对λmax有一致的影响，相对于氢的15 nm的4-Me，30 nm的4-MeO和50 nm的4-Me2N的波长偏移。关键词：光产生的碳正离子，碳正离子寿命，苯乙烯，光质子化。
• Kinetics of nitroxide radical trapping. 2. Structural effects
  作者：V. W. Bowry、K. U. Ingold

  DOI：10.1021/ja00039a006

  日期：1992.6

  Laser flash photolysis and kinetic competition product studies have demonstrated that in isooctane at ambient temperatures the rate constant for coupling of carbon-centered radicals with persistent nitroxides, k T , depends upon the degree of steric hindrance to coupling and upon the extent of resonance stabilization of the carbon radical. Sterically induced reductions in the magnitude of k T are observed

  激光闪光光解和动力学竞争产物研究表明，在环境温度下，在异辛烷中，以碳为中心的自由基与持久性氮氧化合物的偶联速率常数 k T 取决于偶联的空间位阻程度和共振稳定的程度。碳自由基。对于氮氧化合物结构和碳自由基结构的变化，观察到 k T 大小的空间诱导减少。因此，对于任何特定的碳基，k T 对于 Bredt 规则保护的氮氧化物、9-氮杂双环 [3.3.1] 壬烷-N-氧基 (ABNO) 和去甲托烷-N-氧基而言是最大的，而对于通常的'二叔-烷基氮氧化物 k T 沿系列递减，1,1,3,3-四甲基异碘啉-2-氧基≥2,2,5,5-四甲基哌啶-1-氧基（Tempo）>二叔丁基氮氧化物，i．
• Dynamics of radical pair reactions in micelles
  作者：I. R. Gould、M. B. Zimmt、Nicholas J. Turro、B. H. Baretz、G. F. Lehr

  DOI：10.1021/ja00302a001

  日期：1985.8

  On etudie par photolyse laser pulsee le comportement des radicaux phenyl-1 ethyle, cumyle et diphenyl-methyle solubilises dans des micelles de lauryl sulfate de Na et de chlorure de palmityl trimethylammonium

  在 etudie par 光解激光脉冲 le comportement des radicaux phenyl-1ethyle, cumyle et diphenyl-methyle