1-pentafluorophenyl-2-phenylacetylene | 13509-88-1

• 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-pentafluorophenyl-2-phenylacetylene
• 英文别名: 1,2,3,4,5-pentafluoro-6-(phenylethynyl)benzene；(Pentafluorphenyl)phenylacetylen；Phenylaethinyl-pentafluorbenzol；1,2,3,4,5-Pentafluoro-6-(2-phenylethynyl)benzene
• CAS: 13509-88-1
• 化学式: C₁₄H₅F₅
• 分子量: 268.186
• InChiKey: BYKJIXWANUDHRW-UHFFFAOYSA-N

物化性质

• 熔点：
  93 °C
• 沸点：
  289.9±40.0 °C(Predicted)
• 密度：
  1.41±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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-pentafluorophenyl-2-phenylacetylene 在 正丁基锂 、 二氯二茂锆 、 二氯化二硫 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 6.0h， 以76%的产率得到3,4-Bis-pentafluorophenyl-2,5-diphenyl-thiophene
  参考文献：
  名称：

  Regioselective Coupling of Pentafluorophenyl Substituted Alkynes:  Mechanistic Insight into the Zirconocene Coupling of Alkynes and a Facile Route to Conjugated Polymers Bearing Electron-Withdrawing Pentafluorophenyl Substituents

  摘要：

  The reaction of Cp2ZrCl2 with 2 equiv of BuLi at -78 degreesC, followed by the addition of an unsymmetrical tetra- or pentafluorophenyl substituted alkyne R(1)CdropCAr(dagger) (R-1, Ar-dagger = (CH2)(4)Me, p-C6F4H; Me, p-C6F4H; Ph, C6F5), resulted in regioselective couplings of these alkynes to zirconacyclopentaclienes in which the Art substituents preferentially adopt the 3,4-positions (betabeta) of the zirconacyclopentacliene ring. With Cp2Zr(py)(Me3SiC=CSiMe3) as the zirconocene reagent, the couplings could be carried out at room temperature; however, at higher temperatures significant quantities of the 2,4-fluoroaryl substituted (alphabeta) isomers were also formed. None of the conditions employed produced the 2,5-fluoroaryl substituted (alphaalpha) isomers. These fluoroaryl-substituted zirconacyclopentadienes were readily converted to butadienes via reactions with acids. The zirconacyclopentacliene Cp2ZrC4-2,5-Ph-2-3+(C6F5)(2), which resulted from the coupling of PhCequivalent toC(C6F5), was converted to the corresponding thiophene by reaction with S2Cl2, and to an arene by reaction with MeO2CC=CCO2Me/CuCl. Mechanistic studies on zirconocene couplings of (p-CF3C6H4)Cequivalent toC(p-MeC6H4) indicate that the observed regioselectivities are determined by an electronic factor that controls the orientation of at least one of the two alkynes as they are coupled. Additionally, these studies suggest an unsymmetrical transition state for the zirconocene coupling of alkynes, and this is supported by DFT calculations. The reaction of [(C6F5)Cequivalent toCCH(2)](2)CH2 with Cp2Zr(py)(Me(3)SiCequivalent toCSiMe(3)) resulted in a zirconacyclopentacliene in which the pentafluorophenyl substituents have been forced into the 2,5-positions (alphaalpha). Zirconocene coupling of the diyne (C6F5)Cequivalent toC-1+C6H4-Cequivalent toC(C6F5) provided a route to conjugated polymers bearing electron-withdrawing pentafluorophenyl groups.

  DOI：

  10.1021/ja0209161
• 作为产物：
  描述：

  Pentafluorbenzoylbenzylidentriphenylphosphoran 80.0 ℃ 、1.33 kPa 条件下， 生成 1-pentafluorophenyl-2-phenylacetylene
  参考文献：
  名称：

  Bis(pentafluorophenyl)acetylene and 2,3,4,5,6-pentafluorodiphenylacetylene

  摘要：

  DOI：

  10.1021/jo01285a089

文献信息

• Pd-Tetrahydrosalan-Type Complexes as Catalysts for Sonogashira Couplings in Water: Efficient Greening of the Procedure
  作者：Krisztina Voronova、Levente Homolya、Antal Udvardy、Attila C. Bényei、Ferenc Joó

  DOI：10.1002/cssc.201402147

  日期：2014.8

  diphenylacetylenes can be isolated in 76–98 % yield. The aqueous catalyst solution can be recycled four times with decreasing activity; however, yields between 93 and 98 % can still be achieved with extended reaction times. Several water‐insoluble products can be isolated in excellent yield by simple filtration and purification by washing with water; this method is used, for the first time, for this type

  合成了新的磺化四氢salen型配体及其水溶性钯（II）配合物。钯（II）配合物催化各种芳基卤化物（包括氯代芳烃）与末端炔烃的Sonogashira偶联（23个实例），在温和条件下（80°C，空气，无Cu I助催化剂）在有机水溶液中具有良好至优异的转化率混合物和周转频率高达2790 h -1。在优化的反应条件下，以最小化环境污染，可以分离出76.98％的二苯乙炔。催化剂水溶液可以降低活性地循环使用四次。但是，延长反应时间仍可实现93％至98％的收率。通过简单的过滤和水洗纯化，可以分离出几种不溶于水的产物，收率很高。这种方法首次用于这种CC耦合过程。
• Structural eludication of some new titanacycles by means of degradation and 13C NMR studies
  作者：J. Mattia、D.J. Sikora、D.W. Macomber、M.D. Rausch、J.P. Hickey、G.D. Friesen、L.J. Todd

  DOI：10.1016/s0022-328x(00)82951-4

  日期：1981.6

  4-di(pentafluorophenyl)titanole. The latter product can also be obtained in 77% yield from a reaction between titanocene dicarbonyl and phenyl(pentafluorophenyl)acetylene in hexane solution. Application of 13C NMR spectroscopy to the structural elucidation of these and related metallacycles is discussed.

  在回流的苯diphenyltitanocene和苯基（五氟苯基）乙炔之间的反应产生1,1-双（η 5 -环戊二烯基）-2-苯基-3-（五氟苯基），44％收率benzotitanole。用HCl / CHCl 3降解产物，得到二茂钛二氯化物和Z -1,2-二苯基-1-（五氟苯基）乙烯。diphenyltitanocene和苯基的反应（五氟苯基）乙炔苯下光解条件导致1,1-双（η的独家形成5 -环戊二烯基）-2,5-二苯基-3,4-二（五氟苯基）titanole。后者的产物也可以从二茂钛二羰基与苯基（五氟苯基）乙炔在己烷溶液中的反应中以77％的产率获得。应用13讨论了这些和相关金属环的结构解析的13 C NMR光谱学。
• Copper-Catalyzed Aerobic Oxidative Transformation of Ketone-Derived<i>N</i>-Tosyl Hydrazones: An Entry to Alkynes
  作者：Xianwei Li、Xiaohang Liu、Huoji Chen、Wanqing Wu、Chaorong Qi、Huanfeng Jiang

  DOI：10.1002/anie.201405058

  日期：2014.12.22

  A novel strategy involving Cu‐catalyzed oxidative transformation of ketone‐derived hydrazone moiety to various synthetic valuable internal alkynes and diynes has been developed. This method features inexpensive metal catalyst, green oxidant, good functional group tolerance, high regioselectivity and readily available starting materials. Oxidative deprotonation reactions were carried out to form internal

  已开发出一种新的策略，涉及铜催化的酮衍生部分转化为各种合成的有价值的内部炔烃和二炔。该方法的特点是廉价的金属催化剂，绿色氧化剂，良好的官能团耐受性，高区域选择性和易于获得的原料。进行氧化去质子反应以形成内部炔烃和对称二炔。进行hydr与卤化物和末端炔的交叉偶联反应，得到官能化的炔和不对称的共轭二炔。提出了通过碳卡宾中间体进行CC三键形成的机理。
• Synthesis of 1-Azaazulenes from Cycloheptatrienylmethyl Ketone<i>O</i>-Pentafluorobenzoyloximes by Palladium-Catalyzed Cyclization and Oxidation
  作者：Shunsuke Chiba、Mitsuru Kitamura、Osamu Saku、Koichi Narasaka

  DOI：10.1246/bcsj.77.785

  日期：2004.4

  Various 1-azaazulenes are synthesized from cycloheptatrienylmethyl ketone O-pentafluorobenzoyloximes by treatment with a catalytic amount of Pd(dba)2–t-Bu3P (dba = dibenzylideneacetone) and triethy...

  通过用催化量的 Pd(dba)2–t-Bu3P（dba = 二亚苄基丙酮）和三乙醚处理，从环庚三烯基甲基酮 O-五氟苯甲酰肟合成各种 1-氮杂环...
• Nickel- and Copper-Catalyzed Direct Alkynylation of Azoles and Polyfluoroarenes with Terminal Alkynes under O₂ or Atmospheric Conditions
  作者：Naoto Matsuyama、Masanori Kitahara、Koji Hirano、Tetsuya Satoh、Masahiro Miura

  DOI：10.1021/ol100699g

  日期：2010.5.21

  The direct C−H alkynylation of azoles with terminal alkynes proceeds efficiently under a nickel/O2 catalytic system. On the other hand, a copper/air catalyst enables the coupling of polyfluoroarenes with terminal alkynes. These catalyses provide new accesses to arylacetylenes through the formal direct Sonogashira coupling.

  在镍/ O 2催化体系下，唑类与末端炔烃的直接CH炔基化反应有效进行。另一方面，铜/空气催化剂能够使多氟芳烃与末端炔烃偶联。这些催化剂通过正式的直接Sonogashira偶联为芳基乙炔提供了新的途径。