diethyl phenylmaleate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: diethyl phenylmaleate
• 英文别名: diethyl 2-phenylfumarate；Diethyl 2-phenylbut-2-enedioate
• 化学式: C₁₄H₁₆O₄
• 分子量: 248.279
• InChiKey: DUOZXYGXDVYQHT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  环丁醇 、 diethyl phenylmaleate 在 cerium(III) chloride 、 9,10-二联苯蒽 、 四丁基氯化膦 、 对甲苯磺酸 作用下， 以 苯甲腈 为溶剂， 反应 36.0h， 生成 ethyl 7-oxo-8-phenyl-6-oxabicyclo[3.2.1]octane-8-carboxylate 、 ethyl 7-oxo-8-phenyl-6-oxabicyclo[3.2.1]octane-8-carboxylate
  参考文献：
  名称：

  Cerium-Catalyzed Formal Cycloaddition of Cycloalkanols with Alkenes through Dual Photoexcitation

  摘要：

  We describe a synergistic utilization of cerium photocatalysis and photoinduced electron transfer catalysis that enables an atom- and step-economical ring expansion of readily available cycloalkanols. This operationally simple protocol provides rapid access to privileged and synthetically challenging bridged lactones. The mild catalytic manifold has been adapted to continuous flow for scale-up applications and employed for the concise synthesis of polycyclic core of nepalactones.

  DOI：

  10.1021/jacs.8b08781
• 作为产物：
  描述：

  丙二酸二乙酯 、 hydrobenzamide 在 aluminum oxide 作用下， 以 环己烷 为溶剂， 反应 14.83h， 以91%的产率得到diethyl phenylmaleate
  参考文献：
  名称：

  一种羧苄西林钠药物中间体亚苄基丙二酸二乙酯的合成方法

  摘要：

  一种羧苄西林钠药物中间体亚苄基丙二酸二乙酯的合成方法，包括如下步骤：在反应容器中加入丙二酸二乙酯1.3mol,苯甲胺醇溶液1.6--1.9mol,环己烷500ml,氧化铝1.5mol,甲苯200ml,升高溶液温度至80--85℃，回流5--8h,降低溶液温度至60--65℃，继续反应80--110min,降低溶液温度至10--17℃，静置2--5h，溶液分层，取出油层，草酸溶液洗涤，亚硫酸钾溶液洗涤，用二甲苯溶液提取5--7次，合并提取液，脱水剂脱水，减压蒸馏，收集110--117℃的馏分，在乙腈中重结晶，得晶体亚苄基丙二酸二乙酯。

  公开号：

  CN105566109A

文献信息

• Tetraphosphine/palladium-catalyzed Heck reactions of aryl halides with disubstituted alkenes
  作者：Isabelle Kondolff、Henri Doucet、Maurice Santelli

  DOI：10.1016/j.tetlet.2003.09.092

  日期：2003.11

  cyclopentane/[PdCl(C3H5)]2 efficiently catalyses the Heck reaction of disubstituted alkenes such as methyl crotonate, ethyl cinnamate, methyl methacrylate or α-methylstyrene with a variety of aryl halides. In the presence of 1,2-disubstituted alkenes the stereoselectivities of the reactions strongly depend on the substituents of the alkenes. Selectivities up to 97% in favor of E-isomers can be obtained

  顺式，顺式，顺式-1,2,3,4-四（二苯基膦甲基）环戊烷/ [PdCl（C 3 H 5）] 2有效催化巴豆酸甲酯，肉桂酸乙酯，甲基丙烯酸甲酯或α等二取代烯烃的Heck反应-甲基苯乙烯与各种芳基卤化物。在1，2-二取代的烯烃的存在下，反应的立体选择性强烈取决于烯烃的取代基。添加到巴豆酸甲酯中可以得到高达97％的选择性，有利于E-异构体。用1，1-二取代的烯烃获得甲基丙烯酸甲酯或α-甲基苯乙烯的产物混合物。
• Catalytic cross-coupling of diazo compounds with coinage metal-based catalysts: an experimental and theoretical study
  作者：Ivan Rivilla、W. M. C. Sameera、Eleuterio Alvarez、M. Mar Díaz-Requejo、Feliu Maseras、Pedro J. Pérez

  DOI：10.1039/c2dt32439c

  日期：——

  We examined the ability of TpxM (Tpx = hydrotris(pyrazolyl)borate ligand; M = Cu and Ag) and IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene; M = Cu, Ag, Au) complexes as catalyst precursors for the cross-coupling of diazo compounds. Experimental data showed that the metal centre can be tuned with the appropriate selection of the ligand to yield either the homo- or hetero-coupling (cross-coupling)

  我们检查了Tp x M（Tp x =氢三（吡唑基）硼酸酯配体； M =铜和银）和IPrMCl（IPr = 1,3-双（二异丙基苯基）咪唑-2-亚基； M = Cu，Ag， Au）络合物作为重氮化合物交叉偶联的催化剂前体。实验数据表明，该金属中心可以与配体的适当的选择，以产生任一同源或异源偶联（交叉耦合）的产品来调整。通过对反应机理的计算研究，合理化了实验反应模式，并确定了控制选择性的关键反应步骤：金属碳烯中间体与一种重氮化合物之间的初始反应。
• Synthesis of α,β-Alkynyl Esters and Unsymmetrical Maleate Esters Catalyzed by Pd/C; An Efficient Phosphine-Free Catalytic System for Oxidative Alkoxycarbonylation of Terminal Alkynes
  作者：Bhalchandra Bhanage、Sandip Gadge

  DOI：10.1055/s-0032-1316896

  日期：——

  Pd/C-catalyzed oxidative alkoxycarbonylation of terminal alkynes using alcohols in the presence of tetrabutylammonium iodide under CO/O-2 (5:1 atm) has been investigated. The desired alpha,beta-alkynyl esters and unsymmetrical maleate esters are formed in good to excellent yields under different reaction conditions. The present protocol eliminates the use of phosphine ligands and has straightforward catalyst recovery. The catalyst was recycled up to six times without significant loss of catalytic activity.
• A Novel Stereoselective Synthesis of Maleate Derivatives via Palladium-Catalyzed Dicarboalkoxylation of Terminal Alkynes
  作者：Jinheng Li、Huanfeng Jiang、Lanqi Jia

  DOI：10.1080/00397919908086012

  日期：1999.11

  Alkynes were dicarboalkoxylated efficiently and stereoselectively in high yields reacting for about 2h under atmospheric pressure of carbon monoxide at room temperature using a catalytic amount of PdCl2 and a stoichiometric amount of CuCl2.
• High-Speed, Highly Fluorous Organic Reactions
  作者：Kristofer Olofsson、Sun-Young Kim、Mats Larhed、Dennis P. Curran、Anders Hallberg

  DOI：10.1021/jo982511y

  日期：1999.6.1