1-fluoro-4-(3,3,3-trifluoroprop-1-yn-1-yl)benzene | 943-71-5

• 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-fluoro-4-(3,3,3-trifluoroprop-1-yn-1-yl)benzene
• 英文别名: 3,3,3-Trifluoro-1-propynyl-p-fluorobenzene；1-fluoro-4-(3,3,3-trifluoroprop-1-ynyl)benzene
• CAS: 943-71-5
• 化学式: C₉H₄F₄
• 分子量: 188.124
• InChiKey: NOTQKOYZFSFBLQ-UHFFFAOYSA-N

物化性质

• 沸点：
  141-142 °C
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-fluoro-4-(3,3,3-trifluoroprop-1-yn-1-yl)benzene 在 1,3-双(二苯基膦)丙烷 、 zinc(II) iodide 、 iron(II) chloride 、 锌 作用下， 以 乙腈 为溶剂， 反应 36.0h， 以96%的产率得到
  参考文献：
  名称：

  Iron-catalyzed [2 + 2 + 2] cycloaddition of trifluoromethyl group substituted unsymmetrical internal alkynes

  摘要：

  用铁催化的[2 + 2 + 2]分子间环加成反应，三氟甲基取代的非对称内部炔烃得到相应的三氟甲基取代苯衍生物，收率高，选择性优异。

  DOI：

  10.1039/c4ra06973k
• 作为产物：
  描述：

  trifluoromethylcopper(I) 、 (4-氟苯基乙炔)三甲基硅烷 在 氧气 、 四甲基乙二胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 19.0h， 以15 mg的产率得到1-fluoro-4-(3,3,3-trifluoroprop-1-yn-1-yl)benzene
  参考文献：
  名称：

  Fluoroform-Derived CuCF₃ for Trifluoromethylation of Terminal and TMS-Protected Alkynes

  摘要：

  An efficient trifluoromethylation reaction of alkynes using a fluoroform-derived CuCF3 reagent is described. The CF3 source is the inexpensive industrial waste fluoroform (CF3H). The air-stable CuCF3 reagent can be prepared in large quantities and is convenient to use. Synthetically useful trifluoromethylated alkynes containing a wide range of functional groups were successfully synthesized under mild conditions. Both terminal and TMS-protected alkynes gave the products in one step. The beneficial effect of a diamine ligand tetramethylethylenediamine (TMEDA) with the fluoroform-derived CuCF3 reagent was also demonstrated.

  DOI：

  10.1021/acs.orglett.6b00999

文献信息

• Practical Methods for the Synthesis of Trifluoromethylated Alkynes: Oxidative Trifluoromethylation of Copper Acetylides and Alkynes
  作者：Cédric Tresse、Céline Guissart、Stéphane Schweizer、Yassine Bouhoute、Anne-Caroline Chany、Mary-Lorène Goddard、Nicolas Blanchard、Gwilherm Evano

  DOI：10.1002/adsc.201400057

  日期：2014.6.16

  Two practical and complementary methods are reported for the synthesis of trifluoromethylated alkynes. The first one, a mix‐and‐stir process, is based on the oxidative trifluoromethylation of readily available and bench‐stable copper acetylides while the second one, which displays a broad substrate scope and has several advantages over existing procedures, is based on the oxidative copper‐catalyzed

  报道了两种实用和互补的方法用于合成三氟甲基化炔烃。第一种是混合搅拌法，基于易得的和板凳稳定的乙炔铜的氧化三氟甲基化，而第二种基于较广泛的底物范围，并且与现有方法相比具有多个优点，其基础是末端炔烃的氧化铜催化直接三氟甲基化。两种反应均提供了用户友好的三氟甲基化乙炔的合成方法，该方法可轻松地从容易获得的起始原料中获得。
• Direct Synthesis of a Trifluoromethyl Copper Reagent from Trifluoromethyl Ketones: Application to Trifluoromethylation
  作者：Hiroki Serizawa、Kohsuke Aikawa、Koichi Mikami

  DOI：10.1002/chem.201303828

  日期：2013.12.23

  fluorine: The direct synthesis of CuCF3 from a cuprate reagent and trifluoromethyl ketones, as one of the most economical and efficient trifluoromethyl sources, was accomplished. The advantages of this method are all of reagents employed are low‐cost, operation is simple, and the yield of CuCF3 is virtually quantitative (see scheme). Furthermore, three types of trifluoromethylations smoothly proceeded

  用氟经济：由铜酸盐试剂和三氟甲基酮（最经济，最有效的三氟甲基来源之一）直接合成CuCF 3。该方法的优势在于所使用的所有试剂成本低，操作简单且CuCF 3的产率实际上是定量的（请参阅方案）。此外，三种类型的三氟甲基化顺利进行以提供高产率的相应产物。
• Iron-Catalyzed Intermolecular Hydrothiolation of Internal Alkynes with Thiosalicylic Acids, and Sequential Intramolecular Cyclization Reaction
  作者：Taro Sonehara、Shogo Murakami、Sae Yamazaki、Motoi Kawatsura

  DOI：10.1021/acs.orglett.7b01953

  日期：2017.8.18

  We demonstrate the iron-catalyzed intermolecular coupling of internal alkynes and thiosalicylic acid derivatives. The reaction was effectively catalyzed by the Fe(acac)2/1,10-phenanthroline catalyst in toluene/HFIP (hexafluoroisopropyl alcohol) as the reaction solvent and afforded several types of 1,3-oxathiine derivatives in moderate to high yields through the intermolecular hydrothiolation and sequential

  我们证明了内部炔烃和硫代水杨酸衍生物的铁催化的分子间偶联。Fe（acac）2 / 1,10-菲咯啉催化剂在甲苯/ HFIP（六氟异丙醇）中作为反应溶剂有效地催化了该反应，并通过分子间反应以中等至高收率提供了几种类型的1,3-氧代嘧啶衍生物氢硫基化和顺序分子内环化。
• Iridium-Catalyzed Regioselective Synthesis of Trifluoromethylated Isocoumarins through Annulation of Benzoic Acids with Trifluoromethylated Alkynes
  作者：Guangyuan Liu、Guanghua Kuang、Xingxing Zhang、Naihao Lu、Yang Fu、Yiyuan Peng、Yirong Zhou

  DOI：10.1021/acs.orglett.9b00572

  日期：2019.5.3

  An unprecedented Ir-catalyzed oxidative coupling of benzoic acids with trifluoromethylated alkynes was successfully developed to provide diverse trifluoromethylated isocoumarins in moderate to good yields. This new practical procedure was highlighted by mild reaction conditions, broad substrate scope, good regioselectivity, high efficiency, and easy operation.

  成功开发出前所未有的Ir催化的苯甲酸与三氟甲基化炔烃的氧化偶合，以中等到良好的产率提供各种三氟甲基化异香豆素。反应条件温和，底物范围广，区域选择性好，效率高且易于操作，突出了这一新的实用程序。
• Synthesis of trifluoromethyl-group-containing cyclopentadienones by the palladium-catalyzed [2 + 2 + 1] cycloaddition of aryl- and trifluoromethyl-group substituted internal alkynes and carbon monoxide
  作者：Shogo Murakami、Taro Sonehara、Kousuke Iwakami、Hiroaki Tsuji、Motoi Kawatsura

  DOI：10.1016/j.tetlet.2019.01.036

  日期：2019.2

  We investigated the palladium-catalyzed [2 + 2 + 1] cycloaddition of aryl- and trifluoromethyl-group-substituted internal alkynes and carbon monoxide, and revealed that the PdBr2 effectively catalyzed the intended reaction. The PdBr2-catalyzed reaction smoothly proceeded and provided aryl- and trifluoromethyl-group-containing cyclopentadienone derivatives in up to 92% yield.

  我们研究了钯催化的芳基和三氟甲基取代的内部炔烃和一氧化碳的[2 + 2 + 1]环加成反应，并揭示了PdBr 2有效催化了预期的反应。PdBr 2催化的反应顺利进行，并以高达92％的收率提供了含芳基和三氟甲基的环戊二烯酮衍生物。