methyl 4-acetylcinnamate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-acetylcinnamate
• 英文别名: Methyl 3-(4-acetylphenyl)prop-2-enoate
• 化学式: C₁₂H₁₂O₃
• 分子量: 204.225
• InChiKey: CZRVJQFOAJWAPP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  对氯苯乙酮 、 丙烯酸甲酯（MA） 在 sodium carbonate 、 biphenyl-4-yl-[4(5)-(biphenyl-4-yl)-1H-imidazol-2-yl]ketone 、 palladium dichloride 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.0h， 以40%的产率得到methyl 4-acetylcinnamate
  参考文献：
  名称：

  Application of 3-aroyl-4(5)-arylimidazols as efficient ligands in Pd-catalyzed Heck reactions

  摘要：

  卤代芳烃与各种烯烃在0.25 mol%的PdCl_2和0.5 mol%的双苯基-4-基-[4(5)-(双苯基-4-基)-1H-咪唑-2-基]酮2f作为配体，以及Na_2CO_3为最佳碱，在1:1的H_2O/DMF混合溶剂中于80°C反应8小时，成功进行了Heck偶联反应。咪唑2f被发现是一种廉价、空气稳定、易于获取且高效的配体，在钯催化的Heck反应中对碘代芳烃（76%-94%）、溴代芳烃（52%-79%）和氯代芳烃（40%-70%）均有良好效果。

  DOI：

  10.3906/kim-1307-18

文献信息

• Electron-Deficient Phosphines Accelerate the Heck Reaction of Electronrich Olefins in Ionic Liquid
  作者：Shifang Liu、Ourida Saidi、Neil Berry、Jiwu Ruan、Alan Pettman、Nick Thomson、Jianliang Xiao

  DOI：10.2174/157017809787003052

  日期：2009.1.1

  Using various substrates and ligands, we show that electron-deficient, bidentate phosphines are the ligands of choice for palladium-catalyzed arylation of electron-rich olefins. This is in contrast to the reaction of electron-deficient olefins, which benefit from electron-rich monodentate phosphines. A tentative explanation is offered based on DFT calculations.

  使用各种底物和配体，我们证明了缺电子的双齿膦配体是钯催化富电子烯烃芳基化反应的首选配体。这与电子匮乏的烯烃反应相反，后者得益于电子丰富的单齿膦配体。我们根据DFT计算结果提供了一个初步的解释。
• Synthesis, structural characterization and catalytic activity of benzimidazole-functionalized Pd(II) <i>N</i> -heterocyclic carbene complexes
  作者：Yalin Diao、Rong Hao、Junfeng Kou、Mingyu Teng、Guoli Huang、Yegao Chen

  DOI：10.1002/aoc.3030

  日期：2013.9

  Two Pd(II)–NHC complexes bearing benzimidazole and pyridine groups have been successfully prepared and fully characterized by NMR and X‐ray diffraction analysis. The structure of palladium complexes are a typical square‐planar with palladium surrounded by two pairs of trans‐arranged benzimidazole and carbene ligands. The Pd–NHC complexes have been proved to be a highly efficient catalyst for the Mizoroki–Heck

  已经成功制备了两个带有苯并咪唑和吡啶基团的Pd（II）-NHC配合物，并通过NMR和X射线衍射分析对其进行了全面表征。钯配合物的结构是典型的方形平面，钯被两对反式排列的苯并咪唑和卡宾配体包围。已证明Pd-NHC络合物是温和条件下芳基卤化物与各种取代丙烯酸酯的Mizoroki-Heck偶联反应的高效催化剂，产率高。版权所有©2013 John Wiley＆Sons，Ltd.
• Silica-Supported Ni(II)–DABCO Complex: An Efficient and Reusable Catalyst for the Heck Reaction
  作者：Abdol R. Hajipour、Parisa Abolfathi

  DOI：10.1007/s10562-016-1880-9

  日期：2017.1

  interesting nickel-based catalyst supported on DABCO-functionalized silica was successfully prepared and evaluated as heterogeneous nanocatalyst in Heck cross coupling reaction of various aryl halides and methyl acrylate. The as-prepared nanocatalyst was well characterized by FT-IR, FE-SEM, TEM, XRD, SEM-EDX, ICP and TGA techniques and found to be highly efficient in the reaction system in terms of activity

  摘要 成功制备了一种有趣的镍基催化剂，负载在 DABCO 功能化二氧化硅上，并作为多相纳米催化剂在各种芳基卤化物和丙烯酸甲酯的 Heck 交叉偶联反应中进行评估。所制备的纳米催化剂通过 FT-IR、FE-SEM、TEM、XRD、SEM-EDX、ICP 和 TGA 技术得到了很好的表征，并发现在活性和可回收性方面在反应体系中是高效的。图形摘要这项工作提供了一种基于镍纳米颗粒的经济且非均相催化系统，负载在 DABCO 功能化二氧化硅上，用于各种芳基卤化物与丙烯酸甲酯的 Heck 交叉偶联反应。
• An ester appending multifunctional ionic liquid for Pd(II) catalyzed Heck reaction
  作者：Anand D. Sawant、Dilip G. Raut、Nitin B. Darvatkar、Uday V. Desai、Manikrao M. Salunkhe

  DOI：10.1016/j.catcom.2010.10.004

  日期：2010.12

  A basic, ester functionalized, imidazolium based ionic liquid (IL2), 3-Methyl-1-(ethoxycarbonylmethyl)imidazolium hydroxide was designed eyeing in situ generation and stabilization of palladium nanoparticles for palladium catalyzed Heck reaction of haloarenes and olefins. This phosphine-free Pd-IL catalyst demonstrated excellent activity and reusability at relatively low reaction temperature (80 °C)

  一个基本的，酯官能化，咪唑鎓基的离子液体（IL2），3-甲基-1-（乙氧羰基甲基）咪唑鎓氢氧化物被设计虎视眈眈原位生成和钯纳米颗粒的镇定钯催化的Heck卤代芳烃和烯烃的反应。这种无膦的Pd-IL催化剂在较低的反应温度（80°C）下对包括氯代芳烃在内的各种卤代芳烃都表现出出色的活性和可重复使用性。较低的反应温度可归因于原位生成均匀且球形的钯纳米粒子（〜5 nm）。
• Novel bis(azole) pincer palladium complexes: synthesis, structures and applications in Mizoroki–Heck reactions
  作者：Qun-Li Luo、Jian-Ping Tan、Zhi-Fu Li、Yue Qin、Lin Ma、Dong-Rong Xiao

  DOI：10.1039/c0dt01414a

  日期：——

  Two novel NCN-pincer complex precursors bearing frameworks of 2,6-bis(oxazol-4-yl)benzene (A) and 2-(thiazol-4-yl)-6-(oxazol-4-yl)benzene (B) were synthesized. Palladations of A and B afforded two new bis(azole) pincer complexes, [(A-κ3NCN)PdBr] (1) and [(B-κ3NCN)PdBr] (2). Both complexes were fully characterized by NMR, MS, DSC-TGA and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in a noncentrosymmetric orthorhombic space group Cmc21 (No. 36, Z = 4). Complex 2 crystallizes in a centrosymmetric monoclinic space groupP21/n (No. 14, Z = 4). Despite the similarity in their chemical formulas, the structures of the two complexes are subtly different: they are built up of two-dimensional supramolecular layers with identical topology, but stacked in different sequences, i.e., the layers in complex 1 are stacked in an AAAA-type fashion, while those in complex 2 are stacked in an alternating AA−1AA−1 sequence (A denotes a layer; A−1 stands for A's inversion symmetry equivalent). In addition, the complexes showed good catalytic activity toward Mizoroki–Heck reactions.

  合成了两种新型NCN型螯合配体前驱体,其骨架分别为2,6-双(噁唑-4-基)苯(A)和2-(噻唑-4-基)-6-(噁唑-4-基)苯(B),之后对A和B进行铂催化得到两种新型双唑螯合配体配合物,即[(A-κ3 NCN)PdBr](1)和[(B-κ3 NCN)PdBr](2)。两种配合物均通过核磁共振、质谱、差示扫描量热-热重分析和单晶X射线衍射进行了表征。配合物1的晶体属于非对称正交晶系Cmc21(No. 36,Z=4)。配合物2的晶体属于对称单斜晶系P21/n(No. 14,Z=4)。两种配合物的化学式相似,但结构略有不同:它们都是由具有相同拓扑结构但堆叠次序不同的二维层状超分子组成,即配合物1的堆叠次序为AAAA型,而配合2的堆叠次序为AA1 AA1 交替型(A表示一个层;A1表示A的反演对称对等)。另外,这些配合物在 Mizoroki-Heck 反应中表现出良好的催化活性。