六苯乙烷 | 17854-07-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 中文名称: 六苯乙烷
• 英文名称: hexaphenylethane
• 英文别名: gomberg’sdimer；1,1,2,2,2-pentakis-phenylethylbenzene
• CAS: 17854-07-8
• 化学式: C₃₈H₃₀
• 分子量: 486.656
• InChiKey: IPOBVSHPVYWJQC-UHFFFAOYSA-N

物化性质

• 沸点：
  517.52°C (rough estimate)
• 密度：
  1.1245 (estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  10.4
• 重原子数：
  38
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.052
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2902909090

反应信息

• 作为反应物：
  描述：

  六苯乙烷 在 氢化锶 作用下， 以 苯 为溶剂， 反应 4.0h， 生成 bis(triphenylmethyl)strontium
  参考文献：
  名称：

  Nakhmanovich, B. I.; Kristal'nyi, E. V.; Basova, R. V., Doklady Chemistry, 1980, vol. 255, p. 520 - 522

  摘要：

  DOI：
• 作为产物：
  描述：

  三苯基甲醇 在 四氢呋喃 、 trimesitylvanadium 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到六苯乙烷
  参考文献：
  名称：

  芳基钒十一。Zur reaktion von trimsitylvana mit ketonen

  摘要：

  溶液中的Trimesitylvanadium与一系列酮反应。根据酮的结构，这些反应分别产生烯烃，醇或自由基。受阻位酮仅与三苯甲基钒形成配位化合物，或根本不发生反应。

  DOI：

  10.1016/s0022-328x(00)99479-8
• 作为试剂：
  描述：

  、 碘代叔丁烷 在 六苯乙烷 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以91%的产率得到[(N(2-P(CHMe2)2-4-MeC6H3)2)NiI]
  参考文献：
  名称：

  烷基碘与镍（I）单羰基物种CC键形成机理的实验和计算研究

  摘要：

  An open-shell reaction of the nickel(I) carbonyl species (PNP)Ni-CO (1) with iodoalkanes has been explored experimentally and theoretically. The initial iodine radical abstraction by a nickel(I) carbonyl species was suggested to produce (PNP)Ni-I (4) and the concomitant alkyl radical, according to a series of experimental indications involving stoichiometric controls employing iodoalkanes. Corresponding alkyl radical generation was also confirmed by radical trapping experiments using Gomberg's dimer. Molecular modeling supports that the nickel acyl species (PNP)N1-COCH3 (2) can be formed by a direct C-C bond formation between a carbonyl ligand of 1 and a methyl radical. As an alternative pathway, the five-coordinate intermediate species (PNP)Ni(CO) (CH3) (5) that involves both CO and CH3 binding at a nickel(II) center is also suggested with a comparable activation barrier, although this pathway energetically favors the formation of (PNP)Ni-CH3 (3) via a barrierless elimination of CO over a CO migratory insertion. Thus, our present work supports that the direct C-C bond coupling occurs between an alkyl radical and the carbonyl ligand at a monovalent nickel center in the generation of an acyl product.

  DOI：

  10.1021/acs.organomet.5b00548

文献信息

• Reactions of hexacarbonyl derivatives of group 5 metals (V, Nb, Ta) with 9,10-phenanthrenequinone
  作者：F. Calderazzo、G. Pampaloni

  DOI：10.1016/0022-328x(87)80277-2

  日期：1987.8

  vanadium, niobium and tantalum of formula V(C14H8O2)3] (M = V, Nb, Ta) have been prepared: (a) by reaction with PQ of the carbonyl derivatives V(CO)6 and Na[M(CO)6] (M = V, Nb, Ta) and (b) by reaction of the anhydrous metal chlorides VCl3 and M2Cl10 (M = Nb, Ta) with the mono- or the di-anion of PQ. Reaction of Na[M(C14H8O2)3] (M  Nb, Ta) with hydrogen chloride has given the protonated species H[M(C14H8O2)3]

  制备了式V（C 14 H 8 O 2）3 ]（M = V，Nb，Ta）的钒，铌和钽的9,10-菲醌（PQ）衍生物：（a）通过与PQ的PQ反应羰基衍生物V（CO）6和Na [M（CO）6 ]（M = V，Nb，Ta）和（b）通过无水金属氯化物VCl 3和M 2 Cl 10（M = Nb，Ta）反应与PQ的单阴离子或双阴离子。Na [M（C 14 H 8 O 2）3 ]（MNb，Ta）与氯化氢反应，得到质子化物质H [M（C 14 H 8 O 2）2）3 ]。
• Determining the Inherent Selectivity for Carbon Radical Hydroxylation versus Halogenation with Fe^III(OH)(X) Complexes: Relevance to the Rebound Step in Non-heme Iron Halogenases
  作者：Vishal Yadav、Rodolfo J. Rodriguez、Maxime A. Siegler、David P. Goldberg

  DOI：10.1021/jacs.0c00493

  日期：2020.4.22

  The first structural models of the proposed cis-FeIII(OH)(halide) intermediate in the non-heme iron halogenases were synthesized and examined for their inherent reactivity with tertiary carbon radicals. Selective hydroxylation occurs for these cis-FeIII(OH)(X) (X = Cl, Br) complexes in a radical rebound-like process. In contrast, a cis-FeIII(Cl)2 complex reacts with carbon radicals to give halogenation

  合成了非血红素铁卤化酶中提出的 cis-FeIII(OH)(卤化物) 中间体的第一个结构模型，并检查了它们与叔碳自由基的固有反应性。这些 cis-FeIII(OH)(X) (X = Cl, Br) 络合物在自由基反弹样过程中发生选择性羟基化。相反，顺式 FeIII(Cl)2 络合物与碳自由基反应产生卤化作用。这些结果根据酶和相关催化剂中类似的回弹中间体的固有反应性进行了讨论。
• Direct Observation of Oxygen Rebound with an Iron-Hydroxide Complex
  作者：Jan Paulo T. Zaragoza、Timothy H. Yosca、Maxime A. Siegler、Pierre Moënne-Loccoz、Michael T. Green、David P. Goldberg

  DOI：10.1021/jacs.7b07979

  日期：2017.10.4

  Efforts to model the rebound reaction in a synthetic system have been unsuccessful, in part because of the challenge in preparing a suitable metal-hydroxide complex at the correct oxidation level. Herein we report the synthesis of such a complex. The reaction of this species with a series of substituted radicals allows for the direct interrogation of the rebound process, providing insight into this

  烷烃羟基化的反弹机制在 40 多年前就被用来帮助解释细胞色素 P450 的反应模式，随后被用来深入了解一系列生物和合成系统。在合成系统中模拟回弹反应的努力并未成功，部分原因是在正确的氧化水平下制备合适的金属氢氧化物络合物面临挑战。在此，我们报告了这种复合物的合成。该物质与一系列取代基的反应可以直接询问反弹过程，从而深入了解这种统一调用但以前未观察到的过程。
• Aromatic triphenylmethylation reaction between benzoyl peroxides and triphenymethyl in aromatic solvents
  作者：T. Suehiro、A. Kanoya、T. Yamauchi、T. Komori、Shin-Ichi Igeta

  DOI：10.1016/s0040-4020(01)82461-3

  日期：1968.1

  derivatives by the reaction between benzoyl peroxides and triphenylmethyl in aromatic solvents has been studied. Triphenylmethylation of a solvent molecule is a reaction between benzoyloxy sigma complex and triphenylmethyl. This mechanism has been evidenced by the analysis of isomer ratios of o-, m-, and p-methoxytetraphenylmethanes. These isomer ratios were controlled by the ratios of isomeric benzoyloxy-anisole

  研究了过氧化苯甲酰与三苯甲基在芳族溶剂中的反应形成四苯甲烷衍生物。溶剂分子的三苯甲基化是苯甲酰氧基西格玛络合物与三苯甲基之间的反应。这种机制已经通过异构体比例的分析证明ø， -米- ，和p -methoxytetraphenylmethanes。这些异构体比例受异构体苯甲酰氧基-茴香醚sigma配合物的比例控制，该比例受溶剂极性的影响而产生更多的o-和p-异构西格玛复合物。如果溶剂的极性增加，则三苯甲基和苯甲酰氧基显示出离子性质，因此三苯甲基化以离子型发生。
• Chemistry of the thermally generated, molybdenum-centered radicals {η5-C5H5Mo(CO)2L} (L = CO, PPh3)
  作者：Philip R. Drake、Michael C. Baird

  DOI：10.1016/0022-328x(89)88046-5

  日期：1989.3

  compounds [η5-C5H5Mo(CO)2L]2 (L = CO, PPh3) exist in solution solely as the metalmetal bonded dimers. no chemical evidence being found for the presence of small equilibrium amounts of the corresponding monomers η5-C5H5Mo(CO)2L}. However, the latter are readily synthesized via hydrogen atom abstraction by the trityl radical from the hydrides η5-C5H5Mo(CO)2LH. The thus-formed radicals are very reactive and

  与此相反，以他们的铬类似物，化合物[η 5 -C 5 H ^ 5的Mo（CO）2 L] 2（L = CO，PPH 3）存在于溶液中单独用作metalmetal连接的二聚体。无化学证据被发现的小型平衡量的相应单体η的存在5 -C 5 H ^ 5的Mo（CO）2 L}。然而，后者可容易地通过氢原子夺取由三苯甲基从氢化物η自由基合成5 -C 5 H ^ 5的Mo（CO）2LH。如此形成的自由基具有很高的反应性，并且除了二聚作用外，它们还参与了各种原子提取和配体取代反应。对这些反应的产物分布的分析为十七电子中间体的中间体提供了明确的证据。