1,2,3,4,5-五氟-6-[2-(2,3,4,5,6-五氟苯基)乙基]苯 | 853-74-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 中文名称: 1,2,3,4,5-五氟-6-[2-(2,3,4,5,6-五氟苯基)乙基]苯
• 英文名称: 2,2',3,3',4,4',5,5',6,6'-decafluorobibenzyl
• 英文别名: 2,2',3,3',4,4',5,5',6,6'-decafluorodibenzyl；1,2-bis(2,3,4,5,6-pentafluorophenyl)ethane；1,2-Bis(pentafluorophenyl)ethane；1,2-bis(perfluorophenyl)ethane；decafluorodibenzyl；1,2-Bis--aethan；Benzene, 1,1'-(1,2-ethanediyl)bis[2,3,4,5,6-pentafluoro-；1,2,3,4,5-pentafluoro-6-[2-(2,3,4,5,6-pentafluorophenyl)ethyl]benzene
• CAS: 853-74-7
• 化学式: C₁₄H₄F₁₀
• 分子量: 362.17
• InChiKey: QDEBTPSMADCMKH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  2,3,4,5,6-五氟甲苯 在 溴 、 碘 、 magnesium 作用下， 生成 1,2,3,4,5-五氟-6-[2-(2,3,4,5,6-五氟苯基)乙基]苯
  参考文献：
  名称：

  723.多氟芳烃。第四部分 2,3,4,5,6-五氟甲苯及相关化合物

  摘要：

  DOI：

  10.1039/jr9610003719

文献信息

• Flash vacuum pyrolysis over magnesium. Part 1. Pyrolysis of benzylic, other aryl/alkyl and aliphatic halides
  作者：R. Alan Aitken、Philip K. G. Hodgson、John J. Morrison、Adebayo O. Oyewale

  DOI：10.1039/b108663d

  日期：2002.1.23

  Flash vacuum pyrolysis over a bed of freshly sublimed magnesium on glass wool results in efficient coupling of benzyl halides to give the corresponding bibenzyls. Where an ortho halogen substituent is present further dehalogenation gives some dihydroanthracene and anthracene. Efficient coupling is also observed for halomethylnaphthalenes and halodiphenylmethanes while chlorotriphenylmethane gives 4,4′-bis(diphenylmethyl)biphenyl. By using α,α′-dihalo-o-xylenes, benzocyclobutenes are obtained in good yield, while the isomeric α,α′-dihalo-p-xylenes give a range of high thermal stability polymers by polymerisation of the initially formed p-xylylenes. Other haloalkylbenzenes undergo largely dehydrohalogenation where this is possible, in some cases resulting in cyclisation. Deoxygenation is also observed with haloalkyl phenyl ketones to give phenylalkynes as well as other products. With simple alkyl halides there is efficient elimination of HCl or HBr to give alkenes. For aliphatic dihalides this also occurs to give dienes but there is also cyclisation to give cycloalkanes and dehalogenation with hydrogen atom transfer to give alkenes in some cases. For 5-bromopent-1-ene the products are those expected from a radical pathway but for 6-bromohex-1-ene they are clearly not. For 2,2-dichloropropane and 1,1-dichloropropane elimination of HCl occurs but for 1,1-dichlorobutane, -pentane and -hexane partial hydrolysis followed by elimination of HCl gives E,E-, E,Z- and Z,Z- isomers of the dialk-1-enyl ethers and fully assigned 13C NMR data are presented for these. With 6-chlorohex-1-yne and 7-chlorohept-1-yne there is cyclisation to give methylenecycloalkanes and -cycloalkynes. The behaviour of 1,2-dibromocyclohexane and 1,2-dichlorocyclooctane under these conditions is also examined. Various pieces of evidence are presented that suggest that these processes do not involve generation of free gas-phase radicals but rather surface-adsorbed organometallic species.

  在玻璃棉上覆盖一层新升华的镁,进行闪式真空热解,能有效促使苄基卤化物耦合生成相应的联苄。当有邻位卤素取代基存在时,进一步脱卤生成部分二氢蒽和蒽。卤甲基萘和二苯基甲烷也能高效耦合,而三苯基氯甲烷则生成4,4′-双(二苯甲基)联苯。用α,α′-二卤代邻二甲苯可以获得较高产率的苯并环丁烯,而异构的α,α′-二卤代对二甲苯,通过形成的对二甲苯的聚合,可以得到一系列高热稳定性的聚合物。其他卤代烃苯大体上会脱卤化氢,某些情况下能产生环化反应。同样可以观察到,苯基卤代烷烃脱去羰基生成苯乙炔以及其他产物。简单的烷基卤化物则高效地脱去HCl或HBr生成烯烃。脂肪族二卤化物也会发生这一反应生成二烯,但不发生环化反应生成环烷烃,或在某些情况下发生氢原子转移的脱卤反应生成烯烃。5-溴戊-1-烯的产物符合自由基途径的预期,但6-溴己-1-烯并不符合。2,2-二氯丙烷和1,1-二氯丙烷能脱去HCl,但1,1-二氯丁烷、戊烷和己烷则能部分水解,随后脱去HCl,生成E,E-, E,Z-和Z,Z-异构体二烷-1-烯基醚,并且得到了这些物质的13C NMR全归属数据。6-氯己-1-炔和7-氯庚-1-炔能发生环化反应生成亚甲基环烷烃和环炔烃。本文还考察了1,2-二溴环己烷和1,2-二氯环辛烷在上述条件下的行为。本文给出了众多种证据,表明这些反应过程不涉及气相自由基的形成,而是表面吸附的金属有机物种。
• Photochemical Reductive C-C Coupling with a Guanidine Electron Donor
  作者：Sven Wiesner、Petra Walter、Arne Wagner、Elisabeth Kaifer、Hans-Jörg Himmel

  DOI：10.1002/ejoc.201600978

  日期：2016.10

  step of these reactions. Electron-withdrawing as well as -donating substituents at the phenyl group increase the reaction rate. Quantum chemical computations did not reveal any correlation between either the enthalpy or Gibbs free energy of the N–C bond cleavage step and the experimentally determined first-order rate constants. Instead, the structural difference between the excited state generated by

  评估了许多取代的苄基卤化物（15 个例子）与有机电子给体 2,3,5,6-四（四甲基胍基）吡啶的无金属光诱导还原 C-C 偶联反应。根据苄基上的取代基，可实现 50-95% 范围内的 C-C 偶联产物产率。通过最初形成的苄基-吡啶鎓盐的均裂 N-C 键裂解形成的光化学苄基自由基是这些反应的限速步骤。苯基上的吸电子和供电子取代基提高了反应速率。量子化学计算没有揭示 N-C 键裂解步骤的焓或吉布斯自由能与实验确定的一级速率常数之间的任何相关性。反而，
• A Clean and Selective Radical Homocoupling Employing Carboxylic Acids with Titania Photoredox Catalysis
  作者：David W. Manley、John C. Walton

  DOI：10.1021/ol502625w

  日期：2014.10.17

  A titania photoredox catalysis protocol was developed for the homocoupling of C-centered radicals derived from carboxylic acids. Intermolecular reactions were generally efficient and selective, furnishing the desired dimers in good yields under mild neutral conditions. Selective cross-coupling with two acids proved unsuccessful. An intramolecular adaptation enabled macrocycles to be prepared, albeit

  开发了二氧化钛光氧化还原催化方案，用于衍生自羧酸的以C为中心的自由基的均偶联。分子间反应通常是有效的和选择性的，在温和的中性条件下以良好的产率提供了所需的二聚体。与两种酸的选择性交叉偶联证明是不成功的。分子内适应使大环化合物的制备，尽管产量适中。
• Kolbe Carbon−Carbon Coupling Electrosynthesis Using Solid-Supported Bases
  作者：Hitoshi Kurihara、Toshio Fuchigami、Toshiki Tajima

  DOI：10.1021/jo801016f

  日期：2008.9.1

  We have developed a novel electrolytic system for Kolbe carbon-carbon coupling electrosynthesis based on the acid-base reaction between carboxylic acids as a substrate and solid-supported bases. On the basis of the electrolytic system, Kolbe electrolysis of various carboxylic acids was successfully carried out to provide the corresponding homocoupling products in moderate to excellent yields.

  我们已经开发出了一种新型的电解系统，用于基于羧酸（作为底物）和固体支持的碱之间的酸碱反应进行Kolbe碳-碳偶联电合成。在电解系统的基础上，成功地进行了各种羧酸的Kolbe电解，以中等至极好的收率提供了相应的均偶联产物。
• A well-defined low-valent cobalt catalyst Co(PMe₃)₄ with dimethylzinc: a simple catalytic approach for the reductive dimerization of benzyl halides
  作者：Brendan J. Fallon、Vincent Corcé、Muriel Amatore、Corinne Aubert、Fabrice Chemla、Franck Ferreira、Alejandro Perez-Luna、Marc Petit

  DOI：10.1039/c6nj03265f

  日期：——

  halides which proceeds with low catalyst loadings (0.5 to 5 mol%). By synthetizing each cobalt intermediate we demonstrate that reaction proceeds through two single electron transfers (SET) and that dimethylzinc is only involved in the regeneration of the catalytic species.

  本文中，我们报道了钴催化的苄基卤化物的还原均偶联的第一催化形式，其在低催化剂负载量（0.5至5 mol％）下进行。通过合成每种钴中间体，我们证明了反应是通过两个单电子转移（SET）进行的，并且二甲基锌仅参与催化物质的再生。