1,2,3,4,5-五氟-6-(4-甲基苯基)苯 | 14621-04-6

• 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: 1,2,3,4,5-五氟-6-(4-甲基苯基)苯
• 英文名称: 2,3,4,5,6-pentafluoro-4'-methylbiphenyl
• 英文别名: 2,3,4,5,6-pentafluoro-4'-methyl-1,1'-biphenyl；2,3,4,5,6-pentafluoro-4’-methyl-1,1’-biphenyl；1,2,3,4,5-pentafluoro-6-(4-methylphenyl)benzene
• CAS: 14621-04-6
• 化学式: C₁₃H₇F₅
• 分子量: 258.191
• InChiKey: PWMDTYMKSMKJRY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,2,3,4,5-五氟-6-(4-甲基苯基)苯 在 sodium hydroxide 、 potassium permanganate 、 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 sodium carbonate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 四氯化碳 、 水 为溶剂， 反应 52.0h， 生成 4-n-octyloxy-2,3,5,6-tetrafluorobiphenyl-4'-carboxylic acid
  参考文献：
  名称：

  Synthesis and Phase-transition of 4-alkoxycarbonylphenyl 4′-n-alkoxy-2,3,5, 6-tetrafluorobiphenyl-4-carboxylates

  摘要：

  Two new homologous series of compounds containing symmetrically tetrafluorinated phenyl units, 4-[(s)-2-methylbutoxycarbonyl]phenyl and 4-n-pentyloxyphenyl 4'-n-alkoxy-2,3,5,6-tetrafluorobiphenyl-4-carboxylates (n=5-10) have been synthesized from 1-pentafluorophenyl-2-trimethylsilylacetylene as a starting material, and studied by thermal polarizing microscopy. The members of the chiral series display enantiotropic cholesteric and monotropic smectic C (S-C*) phases for n=5-9, and the homolog of n=10 shows enantiotropic smectic C (S-C*), smectic A and cholesteric phases. However, the homologs of the achiral series exhibit enantiotropic nematic and smectic A phases for n=5,7,8 and 9, and the member of n=6 displays only a nematic phase, whereas the homolog of n=10 shows enantiotropic smectic A and monotropic smectic C phases. 4-[(s)-2-methylbutoxycarbonyl]phenyl 4'-n-octyloxy-2',3',5',6'-tetra-fluorobiphenyl-4-carboxylate has also been prepared and found not to be thermotropic mesogen. It is showed by comparison that the symmetrical tetrafluorination of biphenyl has a destabilizing effect on the mesophase, and the effect differs at the different substituted positions.

  DOI：

  10.1080/10587259608034059
• 作为产物：
  描述：

  4-碘甲苯 在 三苯基膦氯金 、 1-pivaloyloxy-1,2-benziodoxol-3(1H)-one 、 异丙基氯化镁 、 silver(l) oxide 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 为溶剂， 反应 51.0h， 生成 1,2,3,4,5-五氟-6-(4-甲基苯基)苯
  参考文献：
  名称：

  多氟芳烃与芳基锗烷的金催化化学选择性偶联和下游多样化

  摘要：

  本报告描述了在芳族 CI、C-Br、C-Cl、C-OTf 和 C-SiMe3 基团存在下多氟芳烃与芳基锗烷的化学选择性偶联，并展示了进一步的下游多样化，以提供丰富的功能化和高度氟化的聚芳烃。该策略依赖于 FnArH 的原位 Umpolung，然后选择性 Au(I)/Au(III) 催化与缺电子或富芳基锗烷偶联，即使存在具有挑战性的邻位取代基，并扩大了当前氧化金催化中与以前难以接近的缺电子/缺电子联芳基化合物的可用耦合空间。

  DOI：

  10.1021/jacs.0c02860

文献信息

• Fluorinated biphenyls from aromatic arylations with pentafluorobenzenediazonium and related cations. Competition between arylation and azo coupling
  作者：Dmitry Kosynkin、T. Michael Bockman、Jay K. Kochi

  DOI：10.1039/a701745f

  日期：——

  High yields of the mixed perfluorinated biaryls (C6F5–Ar) are obtained by the catalytic dediazoniation of the pentafluorobenzenediazonium salt (C6F5N2+BF4–) in acetonitrile solutions containing various aromatic substrates (ArH) together with small amounts of iodide salts. Activated (electron-rich) as well as deactivated (electron-poor) arenes are successfully pentafluorophenylated by this method. The arylation is distinct from the azo coupling of the same substrates, which takes place in the absence of the iodide catalyst and yields the corresponding diazene (C6F5NN–Ar) as product. The catalytic role of iodide, and the isomeric product distributions obtained with this procedure indicate that the arylation proceeds via the pentafluorophenyl radical in a efficient homolytic chain process. Since azo coupling involves electrophilic aromatic substitution of electron-rich ArH by C6F5N2+, the two competing pathways are distinct and do not have reactive intermediates in common.

  通过催化脱重氮化反应，在含有各种芳香族底物（ArH）及少量碘化盐的乙腈溶液中，五氟苯重氮盐（ N2+BF4–）能够高效生成混合全氟联苯（C6F5–Ar），产率较高。无论是活化的（电子富集的）还是去活化的（电子贫乏的）芳香族化合物，都能通过此方法成功实现五氟苯基化。这种芳基化反应与同种底物的偶氮耦合反应截然不同，后者在无碘催化剂存在下进行，产物为相应重氮烯（ NN–Ar）。碘化物在催化中的作用以及由此过程获得的不同异构产物分布表明，芳基化反应是通过高效的均裂链式过程，经由五氟苯基自由基进行的。由于偶氮耦合涉及电子富集的ArH通过亲电芳香取代反应与 N2+的结合，这两种竞争路径是不同的，且没有共同的反应中间体。
• Copper-Catalyzed Decarboxylative Cross-Coupling of Potassium Polyfluorobenzoates with Aryl Iodides and Bromides
  作者：Rui Shang、Yao Fu、Yan Wang、Qing Xu、Hai-Zhu Yu、Lei Liu

  DOI：10.1002/anie.200904916

  日期：2009.11.23

  For copper only: The decarboxylative cross‐coupling of readily accessible and nonvolatile potassium polyfluorobenzoates with aryl iodides and bromides using a copper catalyst provides polyfluorobiaryls and polyfluorostilbenes in excellent yields (see scheme). Mechanistic analyses are reported for the title reaction.

  仅适用于铜：使用铜催化剂，易于获得且不挥发的多氟苯甲酸钾与芳基碘化物和溴化物的脱羧交叉偶联可提供极佳的收率的多氟联芳基和多氟苯磺酸酯（请参见方案）。报告了标题反应的机理分析。
• Palladium-Catalyzed Solid-State Polyfluoroarylation of Aryl Halides Using Mechanochemistry
  作者：Rikuro Takahashi、Tamae Seo、Koji Kubota、Hajime Ito

  DOI：10.1021/acscatal.1c03731

  日期：2021.12.17

  products. Here, we show that solid-state high-temperature ball-milling conditions facilitate a palladium-catalyzed cross-coupling with polyfluorinated arylboronic acids and pinacol esters employing a simple catalytic system in the absence of any stoichiometric additives. This reaction exhibits a broad substrate scope and can be carried out in air, and the use of large amounts of dry and degassed organic solvents

  多氟化芳基硼亲核试剂和芳基卤化物之间的 Suzuki-Miyaura 交叉偶联能够有效构建有机材料和催化剂中常见的多氟化结构基序。与这种转化相关的一个关键挑战涉及弱亲核多氟化有机硼试剂的缓慢金属转移，这通常会降低偶联产物的产率。在这里，我们展示了固态高温球磨条件促进了钯催化与多氟化芳基硼酸和频哪醇酯的交叉偶联，在没有任何化学计量添加剂的情况下，采用简单的催化体系。该反应底物范围广，可在空气中进行，不需要使用大量干燥脱气的有机溶剂。
• The influence of the nature of phosphine ligand on palladium catalysts for cross-coupling of weakly nucleophilic potassium pentafluorophenyltrifluoroborate with ArHal and PhCH2Hal (Hal=Br, Cl)
  作者：Anton Yu. Shabalin、Nicolay Yu. Adonin、Vadim V. Bardin、Valentin N. Parmon

  DOI：10.1016/j.tet.2014.04.019

  日期：2014.6

  the nature of bulky phosphines used as ligands. As a result, conditions for involving the electron-deficient organoboron reagent—potassium pentafluorophenyltrifluoroborate—in the palladium-catalyzed cross-coupling with aryl bromides and aryl chlorides were identified. It was demonstrated that the chosen conditions are appropriate for the reaction of K[C6F5BF3] with benzyl chloride and benzyl bromide

  研究了配体性质对钯催化剂催化弱亲核性五氟苯基三氟硼酸钾与偶合芳族卤化物ArHal（Hal = Br，Cl）的行为的模仿，该反应亲和力弱的亲核五氟苯基三氟硼酸钾的行为。发现由Pd（OAc）2和合适的含磷配体原位产生的催化剂的活性和反应选择性取决于用作配体的大膦的性质。结果，确定了在钯催化的与芳基溴化物和芳基氯化物的交叉偶联中涉及缺电子的有机硼试剂（五氟苯基三氟硼酸钾）的条件。结果表明，所选择的条件适合于K [C 6F 5 BF 3 ]与苄基氯和苄基溴衍生的五氟苯基芳基甲烷，C 6 F 5 CH 2 Ar。
• An organic cation as a silver(<scp>i</scp>) analogue for the arylation of sp² and sp³ C–H bonds with iodoarenes
  作者：Carlos Arroniz、J. Gabriel Denis、Alan Ironmonger、Gerasimos Rassias、Igor Larrosa

  DOI：10.1039/c4sc01215a

  日期：——

  A general, cost-effective and sustainable replacement for silver in palladium catalysed direct arylations of C(sp²)–H and C(sp³)–H bonds.

  一种通用、具有成本效益且可持续的替代品，用于钯催化的直接芳基化反应中取代银在C(sp²)-H和C(sp³)-H键中的作用。