Diethyl 2-cyanoethylene-1,1-dicarboxylate | 64677-35-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Diethyl 2-cyanoethylene-1,1-dicarboxylate
• 英文别名: diethyl 2-(cyanomethylene)malonate；1,1-diethyl 2-cyanoethenedicarboxylate；ethyl 3-cyano-2-ethoxycarbonylpropenoate；Propanedioic acid, (cyanomethylene)-, diethyl ester；diethyl 2-(cyanomethylidene)propanedioate
• CAS: 64677-35-6
• 化学式: C₉H₁₁NO₄
• 分子量: 197.191
• InChiKey: BKZNMXDYCFWBAN-UHFFFAOYSA-N

物化性质

• 沸点：
  120-126 °C(Press: 1 Torr)
• 密度：
  1.154±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  76.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Diethyl 2-cyanoethylene-1,1-dicarboxylate 在 三氟化硼乙醚 、 2,4,6-三甲基苯磺酰羟胺 、 三乙胺 作用下， 以 乙醚 为溶剂， 以90%的产率得到3-Cyano-aziridine-2,2-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  1 H-氮丙啶的新途径：向亲电子烯烃加成O-亚甲磺酰基羟胺

  摘要：

  O-亚甲基亚磺酰基羟胺（MSH）与亲电烯烃反应，并用三乙胺处理后，形成1 H-氮丙啶。

  DOI：

  10.1039/c39800001038
• 作为产物：
  描述：

  (三苯基膦)乙腈 、 酮基丙二酸二乙酯 以 甲苯 为溶剂， 反应 3.0h， 以81%的产率得到Diethyl 2-cyanoethylene-1,1-dicarboxylate
  参考文献：
  名称：

  利用醇作为氢原子转移剂的铈催化的烷烃的 C-H 官能化

  摘要：

  现代光氧化还原催化传统上依赖于金属多吡啶基配合物的金属到配体电荷转移 (MLCT) 激发，以利用光能来活化有机底物。在这里，我们展示了铈醇盐配合物的配体-金属电荷转移（LMCT）激发的催化应用，以利用丰富且廉价的三氯化铈作为催化剂轻松活化烷烃。正如铈催化的 CH 胺化和烃的烷基化所证明的那样，这种反应歧管可以通过直接访问具有挑战性的烷氧基自由基，轻松地将大量醇用作实用和选择性的氢原子转移 (HAT) 试剂。此外，通过一系列光谱实验研究了 LMCT 激发事件，

  DOI：

  10.1021/jacs.0c00212

文献信息

• Aza-MIRC Reactions of Sulfonyl-Activated Hydroxycarbamates withα,β-Difunctionalised Acrylates
  作者：Stefania Fioravanti、Alberto Morreale、Lucio Pellacani、Paolo A. Tardella

  DOI：10.1002/ejoc.200300425

  日期：2003.12

  high yields (up to 95%) under mild conditions from the reaction of trisubstituted olefins bearing different groups with nosyloxycarbamates in the presence of calcium oxide. We propose a possible explanation for the different reactivities observed between these olefins and the aminating agents. Reagent-controlled stereoselective amination reactions led to the expected products with high conversions and

  在温和条件下，在氧化钙的存在下，由带有不同基团的三取代烯烃与硝基甲氧基氨基甲酸酯的反应容易以高产率（高达 95%）获得高度官能化的氮丙啶。我们对在这些烯烃和胺化剂之间观察到的不同反应性提出了可能的解释。试剂控制的立体选择性胺化反应产生具有高转化率和纯度的预期产物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Lewis Acid Promoted [2 + 1] Cycloaddition Reactions of 1-Seleno-2-silylethene with Tricarbonyl-Substituted Olefins
  作者：Shoko Yamazaki、Hitoshi Kumagai、Takashi Takada、Shinichi Yamabe、Kagetoshi Yamamoto

  DOI：10.1021/jo9622486

  日期：1997.5.1

  tris(alkoxycarbonyl) olefins 2 or 1,1-bis(alkoxycarbonyl)-2-acyl olefins 3 in the presence of ZnBr(2) at -30 degrees C gave cis-substituted cyclopropanes exclusively. The origin of the cis stereochemistry is ascribed to the synclinal addition path of the ZnBr(2)-coordinated electrophilic olefin to 1. Application of the highly functionalized selenium- and silicon-substituted cyclopropane products to the preparation

  已经研究了在路易斯酸存在下1-硒-2-甲硅烷基1与高度亲电的三羰基取代的烯烃的反应。1-（苯基硒代）-2-（三甲基甲硅烷基）乙烯（1a）与三（烷氧羰基）烯烃2或1,1-双（烷氧羰基）-2-酰基烯烃3在ZnBr（2）存在下于- 30℃仅产生顺式取代的环丙烷。顺式立体化学的起源归因于ZnBr（2）配位的亲电烯烃向1的向向加成路径。高官能化的硒和硅取代的环丙烷产品在制备有用的合成中间体20中的应用还证明了拟除虫菊酯类杀虫剂。
• Expedient radical phosphonylations <i>via</i> ligand to metal charge transfer on bismuth
  作者：Jatin Patra、Akshay M. Nair、Chandra M. R. Volla

  DOI：10.1039/d4sc00692e

  日期：——

  bismuth LMCT catalysis for the generation of heteroatom centered radicals, we hereby report an efficient radical phosphonylation using BiCl3 as the LMCT catalyst. Phosphonyl radicals generated via visible-light induced LMCT of BiCl3 were subjected to a variety of transformations like alkylation, amination, alkynylation and cascade cyclizations. The catalytic system tolerated a wide range of substrate classes

  尽管铋成本低且毒性低，但其在有机合成中的应用有限。尽管Bi( III )盐的光活性已得到充分研究，但尚未在光催化中得到有效利用。迄今为止，只有一份关于铋基光催化的报告，其中使用铋上的配体到金属电荷转移（LMCT）产生以碳为中心的自由基。在这方面，为了扩大铋LMCT催化生成杂原子中心自由基的视野，我们在此报告了使用BiCl 3作为LMCT催化剂的有效自由基膦酰化。通过可见光诱导 BiCl 3的 LMCT 产生的膦酰基自由基经历了各种转化，如烷基化、胺化、炔基化和级联环化。该催化系统可耐受多种底物类别，从而提供出色的支架产率。该反应具有可扩展性，并且需要较低的铋催化负载量。进行了详细的机理研究以探讨反应机理。在当前的工作中，多种自由基磷酸化导致形成 sp 3 -C–P、sp 2 -C–P、sp-C–P 和 P–N 键，这表明铋作为小分子活化的多功能光催化剂的候选资格。
• Influence of Lewis Acids on the Cycloaddition Reactions of Cyano- and Carbomethoxy-Substituted Olefins
  作者：Warunee Srisiri、Anne Buyle Padias、H. K. Hall

  DOI：10.1021/jo00097a054

  日期：1994.9

  The reactions of electrophilic olefins substituted with cyano and/or carbomethoxy groups with donor olefins are investigated. The donor olefins include, in order of decreasing donor character, phenyl vinyl sulfide, isobutyl vinyl ether, tert-butyldimethylsilyl vinyl ether, p-methoxy- and p-methylstyrene, and styrene. The reactions vary ii om [2 + 2] cycloadditions to Diels-Alder reactions to spontaneous free radical copolymerizations. The course of the reaction is determined by both the electron disparity between the two reacting olefins and by the substitution pattern on the electrophilic olefin. Lewis acids (ZnCl2 or ethereal LiClO4) are added to form complexes with the acceptor olefins, resulting in a larger electron disparity between the reactants. With the highly electrophilic olefins with gem-dicyano groups, such as tetracyanoethylene, dimethyl 1,1-dicyanoethylene-2,2-dicarboxylate, and methyl beta,beta-dicyanoacrylate, [2 + 2] cycloadditions occur at room temperature, except for the reaction of TCNE with styrene which has to be carried out in 5 M ethereal LiClO4. With olefins containing one cyano and one carbomethoxy group on the same carbon, dimethyl dicyanofumarate and dimethyl cyanofumarate, inverse electron demand Diels-Alder cycloaddition involving the ester substituent dominates in reactions with the most nucleophilic olefins. The [2 + 2] cycloadducts can be obtained in the presence of Lewis acid. With olefins with two carbomethoxy-substituents on the same carbon, dimethyl 2-cyanoethene-1,1-dicarboxylate and trimethyl ethylenetricarboxylate, the reactions are much slower, and [2 + 4] cycloaddition dominates with the most reactive donor olefins, while the [2 + 2] cycloadduct can be obtained in the presence of Lewis acid. With several acceptor olefins, free radical copolymerizations compete with the cycloadditions when reacted with the least reactive donor olefins. The reaction tendencies are discussed in light of the electron disparity between the olefins. The influence of the Lewis acid on the conformational equilibria and on the reaction course is also addressed.
• Lewis Acid Promoted Reactions of Ethenetricarboxylates with Allenes: Synthesis of Indenes and γ-Lactones via Conjugate Addition/Cyclization Reaction
  作者：Shoko Yamazaki、Yuko Yamamoto、Yugo Fukushima、Masachika Takebayashi、Tetsuma Ukai、Yuji Mikata

  DOI：10.1021/jo1009855

  日期：2010.8.6

  Indenes are important core structures in organic chemistry. Few simple arylallenes have been used to construct indene skeletons by Friedel Crafts reaction. Lewis acid catalyzed reaction of ethenetricarboxylates 1 and arylallenes has been examined in this study. The reaction of arylallenes and ethenetricarboxylate triesters with SnCl4 gave indene derivatives efficiently, via a conjugate addition/Friedel-Crafts cyclization reaction. On the other hand, the reactions of 1,1-diethyl 2-hydrogen ethenetricarboxylate and arylallenes or alkylallenes with SnCl4 at -78 degrees C or room temperature and subsequent treatment with Et3N gave gamma-lactones. The reactions of triethyl ethenetricarboxylate and 1,1-dialkylallenes with SnCl4 at room temperature also gave gamma-lactones.