1,4-bis(3-phenyl-1-propyn-3-one)benzene | 52714-30-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 1,4-bis(3-phenyl-1-propyn-3-one)benzene
• 英文别名: 1,4-bis(3-phenyl-3-oxo-1-propynyl)benzene；1,4-bis(phenylcarbonylethynyl)benzene；1,1'-(1,4-phenylene)bis(3-phenylprop-2-yn-1-one)；3,3′-(1,4-phenylene)bis(1-phenylprop-2-yn-1-one)；3,3'-(1,4-Phenylene)bis(1-phenylprop-2-yn-1-one)；3-[4-(3-oxo-3-phenylprop-1-ynyl)phenyl]-1-phenylprop-2-yn-1-one
• CAS: 52714-30-4
• 化学式: C₂₄H₁₄O₂
• 分子量: 334.374
• InChiKey: APLACSVGMBXINH-UHFFFAOYSA-N

物化性质

• 熔点：
  183-185 °C
• 沸点：
  510.3±60.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-bis(3-phenyl-1-propyn-3-one)benzene 在 氢氧化钾 、 水 作用下， 以 苯 为溶剂， 以83%的产率得到1,4-二乙炔基苯
  参考文献：
  名称：

  A method for the preparation of terminal acetylenes

  摘要：

  A new pathway is proposed for the preparation of terminal acetylenes entailing the condensation of acid chlorides with phenylacetylene, isomerization of the acetylenic ketones with displacement of the oxo group and triple bond in the ketoacetylenic fragment, and subsequent alkaline cleavage of the isomerized ketones.

  DOI：

  10.1007/bf00958856
• 作为产物：
  描述：

  1,1'-(1,4-phenylene)bis(3-(diethylamino)-3-phenylprop-2-en-1-one) 在 sodium hydroxide 、 三氯氧磷 作用下， 生成 1,4-bis(3-phenyl-1-propyn-3-one)benzene
  参考文献：
  名称：

  Isomerization of ?-acetylenic ketones

  摘要：

  A method is suggested for isomerization of alpha-acetylenic ketones with migration of the oxo group from position 1 to position 3 and of the triple bond from position 2 to position 1 of the ketoacetylenic fragment; it consists of addition of Et2NH at the triple bond of the ketone, conversion of the adduct to the imminium salt with POCl3, followed by alkaline hydrolysis. The isomerization is achieved in one preparative stage without isolation of intermediate compounds.

  DOI：

  10.1007/bf00958259

文献信息

• Rapid access to unsymmetrical tolanes and alkynones by sequentially palladium-catalyzed one-pot processes
  作者：Alissa C. Götzinger、Thomas. J. J. Müller

  DOI：10.1039/c6ob00483k

  日期：——

  can be rapidly generated in a one-pot fashion via sequential palladium catalysis. Terminal alkynes, formed in situ by protecting-group free palladium-catalyzed coupling of aryl iodides with ethynyl magnesium bromide, are subsequently transformed by Sonogashira coupling with aryl halides or aroyl chlorides to furnish unsymmetrically substituted alkynes in good to excellent yields.

  炔烃以及不对称取代的甲苯（二芳基炔烃）可以通过顺序钯催化以一锅法快速生成。通过保护基的无钯钯催化的芳基碘化物与乙炔基溴化镁的偶合反应原位形成的末端炔烃，随后通过Sonogashira与芳基卤化物或芳酰氯的偶合反应转化为不对称取代的炔烃，收率良好。
• Chemistry of 1,3-diarylpropynones in superacids
  作者：A. V. Vasilyev、S. Walspurger、M. Haouas、J. Sommer、P. Pale、A. P. Rudenko

  DOI：10.1039/b412323a

  日期：——

  In superacids with H0 = −14 to −20, it has been found that 1,3-diarylpropynones ArCCCOAr′ are either protonated on oxygen of carbonyl groups with the formation of stable ions ArCCC(O+H)Ar′ or undergo further transformations when the highly conjugated system is electron-rich enough. In the latter case, 3-arylindenones are produced very rapidly and with high efficiency (up to 95% yield in less than 30 min). The influence of the substituents Ar, Ar′ and of the reaction conditions on the behavior of 1,3-diarylpropynones and on the intramolecular cyclisation have been studied. From the collected data, a mechanism has been proposed involving vinyl cations ArC+=CHCOAr′ and/or dications ArC+=CHC(O+H)Ar′.

  在pH值为−14至−20的超酸中，发现1,3-二芳基丙炔酮ArCCCOAr′可以通过羰基氧的质子化形成稳定的离子ArCCC(O+H)Ar′，或者当高度共轭体系的电子丰富时发生进一步转化。在后者的情况下，3-芳基茚酮非常迅速且高效地生成（在不到30分钟内产率可达95%）。对取代基Ar、Ar′和反应条件对1,3-二芳基丙炔酮行为以及分子内环化的影响进行了研究。根据收集的数据，提出了一种机制，涉及乙烯基阳离子ArC+=CHCOAr′和/或二阳离子ArC+=CHC(O+H)Ar′。
• Novel (N-heterocyclic carbene)Pd(pyridine)Br₂ complexes for carbonylative Sonogashira coupling reactions: Catalytic efficiency and scope for arylalkynes, alkylalkynes and dialkynes
  作者：Mansur Ibrahim、Imran Malik、Waseem Mansour、Muhammad Sharif、Mohammed Fettouhi、Bassam El Ali

  DOI：10.1002/aoc.4280

  日期：2018.4

  New N,N′‐substituted imidazolium salts and their corresponding dibromidopyridine–palladium(II) complexes were successfully synthesized and characterized. Reactions of palladium bromide with the newly synthesized N,N′‐substituted imidazolium bromides (2a and 2b) in pyridine afforded the corresponding new N‐heterocyclic carbene pyridine palladium(II) complexes (3a and 3b) in high yields. Their single‐crystal

  新的N，N ′取代的咪唑鎓盐及其相应的二溴咪吡啶-钯（II）配合物已成功合成和表征。溴化钯与新合成的N，N'-取代的咪唑鎓溴化物（2a和2b）在吡啶中的反应以高收率提供了相应的新型N-杂环卡宾吡啶钯（II）配合物（3a和3b）。它们的单晶X射线结构显示出扭曲的正方形平面几何形状，其中的卡宾和吡啶配体处于反式位置。两种配合物在芳基碘化物和芳基二碘化物与芳基炔，烷基炔和二炔的羰基化Sonogashira偶联反应中均显示出高催化活性。
• Formation of Active Cyclic Five‐membered Frustrated Phosphane/Borane Lewis Pairs and their Cycloaddition Reactions
  作者：Shunxi Dong、Constantin G. Daniliuc、Gerald Kehr、Gerhard Erker

  DOI：10.1002/chem.201904919

  日期：2020.1.13

  The cyclic five-membered frustrated phosphane/borane Lewis pairs 11 a, b featuring the bulky octaethylhydrindacenyl- (Eind) substituent or its mono-bromo derivative (Br Eind) at phosphorus are monomeric at room temperature. The reactive frustrated Lewis pairs (FLPs) cleave dihydrogen. The cyclic FLP 11 b (Br Eind) undergoes 1,2-P/B addition to ethylene to give the zwitterionic heteronorbornane derivative 14 b

  在磷原子上具有庞大的八乙基氢化茚基-（Eind）取代基或其单溴衍生物（Br Eind）的环状五元受阻膦/硼烷路易斯对11a，b在室温下为单体。反应性沮丧的路易斯对（FLP）裂解二氢。环状FLP 11b（Br Eind）与乙烯进行1,2-P / B加成，得到两性离子杂降冰片烷衍生物14b。它与降冰片烯的碳-碳双键反应相似。在使用多种有机π试剂的情况下，环状FLP 11b经常会经历类似于Alder-Rickert反应的反应序列：环加成反应之后是快速的环还原反应，通过乙烯的挤出形成了新的五元杂环FLP产物。11 b与苯甲醛或与乙炔的反应遵循该反应模式。
• Extended Version of the Corey–Chaykovsky Reaction: Synthesis of 2,4-Substituted Furans by the Treatment of β-Dialkylamino Chalcones with Dimethylsulfonium Methylide
  作者：Roman O. Shcherbakov、Danil A. Myasnikov、Igor V. Trushkov、Maxim G. Uchuskin

  DOI：10.1021/acs.joc.3c00203

  日期：2023.7.7

  We describe the synthesis of functionalized furans using the concept of the extended Corey–Chaykovsky reaction. Namely, β,β-disubstituted α,β-unsaturated ketones were treated with dimethylsulfonium methylide to give vinyloxiranes, which immediately rearranged into the corresponding furans. The developed approach allows for synthesizing a broad range of unsymmetrically di- and trisubstituted furans

  我们使用扩展的 Corey-Chaykovsky 反应的概念描述了功能化呋喃的合成。即，β,β-二取代的α,β-不饱和酮用二甲基锍甲基化物处理得到乙烯基环氧乙烷，其立即重排成相应的呋喃。所开发的方法可以合成各种核心含有各种官能团的不对称二取代和三取代呋喃。