2-(1-Ethyl-propyliden)-2-cyan-essigsaeure-methylester | 22863-91-8

• 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: 2-(1-Ethyl-propyliden)-2-cyan-essigsaeure-methylester
• 英文别名: methyl 2-cyano-3-ethylpent-2-enoate；3-ethyl-2-cyano-pent-2-enoic acid methyl ester；3-Aethyl-2-cyan-pent-2-ensaeure-methylester；(1-Aethyl-propyliden)-malonsaeure-methylester-nitril；2-Aethyl-buten-(1)-dicarbonsaeure-(1.1)-methylester-nitril；(1-Aethyl-propyliden)-cyanessigsaeure-methylester
• CAS: 22863-91-8
• 化学式: C₉H₁₃NO₂
• 分子量: 167.208
• InChiKey: CBTLFZLWZMMGSK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(1-Ethyl-propyliden)-2-cyan-essigsaeure-methylester 在 N-溴代丁二酰亚胺(NBS) 、 过氧化苯甲酰 作用下， 以 四氯化碳 为溶剂， 反应 3.0h， 生成 1-Cyano-2-(dimethoxy-phosphoryl)-2-ethyl-3-methyl-cyclopropanecarboxylic acid methyl ester
  参考文献：
  名称：

  通过迈克尔诱导闭环 (MIRC) 反应合成取代的环丙基膦酸酯

  摘要：

  通过迈克尔诱导的亚磷酸三烷基酯与相应的β-溴亚烷基氰基乙酸酯和丙二酸酯的闭环，以中等至良好的产率制备了多种环丙基膦酸酯。

  DOI：

  10.1055/s-2002-32587
• 作为产物：
  描述：

  3-戊酮 、 氰乙酸甲酯 在 哌啶 作用下， 以 溶剂黄146 为溶剂， 生成 2-(1-Ethyl-propyliden)-2-cyan-essigsaeure-methylester
  参考文献：
  名称：

  通过迈克尔诱导闭环 (MIRC) 反应合成取代的环丙基膦酸酯

  摘要：

  通过迈克尔诱导的亚磷酸三烷基酯与相应的β-溴亚烷基氰基乙酸酯和丙二酸酯的闭环，以中等至良好的产率制备了多种环丙基膦酸酯。

  DOI：

  10.1055/s-2002-32587

文献信息

• Condensation Reactions. I. The Condensation of Ketones with Cyanoacetic Esters and the Mechanism of the Knoevenagel Reaction
  作者：Arthur C. Cope

  DOI：10.1021/ja01290a068

  日期：1937.11
• Masked Cyanoacrylates Unveiled by Mechanical Force
  作者：Matthew J. Kryger、Mitchell T. Ong、Susan A. Odom、Nancy R. Sottos、Scott R. White、Todd J. Martinez、Jeffrey S. Moore

  DOI：10.1021/ja1008932

  日期：2010.4.7

  Mechanical damage of polymers is often a destructive and irreversible process. However, desirable outcomes may be achieved by controlling the location of chain cleavage events through careful design and incorporation of mechanically active chemical moieties known as mechanophores. It is possible that mechanophores can be used to generate reactive intermediates that can autopolymerize or cross-link, thus healing mechanically induced damage. Herein we report the generation of reactive cyanoacrylate units from a dicyanocyclobutane mechanophore located near the center of a polymer chain. Because cyanoacrylates (which are used as monomers in the preparation of superglue) autopolymerize, the generated cyanoacrylate-terminated polymers may be useful in self-heating polymers. Sonication studies of polymers with the mechanophore incorporated into the chain center have shown that selective cleavage of the mechanophore occurs. Trapping experiments with an amine-based chromophore support cyanoacrylate formation. Additionally, computational studies of small-molecule models predict that force-induced bond cleavage should occur with greater selectivity for the dicyanocyclobutane mechanophore than for a control molecule.
• Synthesis of 4,5 Disubstituted 2-Chloronicotinates
  作者：M. Aadil、G. Kirsch

  DOI：10.1080/00397919308012592

  日期：1993.9

  Vilsmeier Haack reagent was found to react with alkylidenecyanoacetate to afford in one step 4,5 disubstituted 2-chloronicotinates.
• Synthesis of Substituted Cyclopropylphosphonates by Michael Induced Ring Closure (MIRC) Reactions
  作者：Christian V. Stevens、Gino Van Heecke、Carmen Barbero、Krystyna Patora、Norbert De Kimpe、Roland Verhé

  DOI：10.1055/s-2002-32587

  日期：——

  A variety of cyclopropylphosphonates were prepared in moderate to good yields by Michael Induced Ring Closure of trialkyl phosphites with the corresponding β-bromoalkylidene cyanoacetates and malonates.

  通过迈克尔诱导的亚磷酸三烷基酯与相应的β-溴亚烷基氰基乙酸酯和丙二酸酯的闭环，以中等至良好的产率制备了多种环丙基膦酸酯。
• Structure–Mechanochemical Activity Relationships for Cyclobutane Mechanophores
  作者：Matthew J. Kryger、Alexander M. Munaretto、Jeffrey S. Moore

  DOI：10.1021/ja2086728

  日期：2011.11.23

  Ultrasound activation of mechanophores embedded in polymer backbones has been extensively studied of late as a method for realizing chemical reactions using force. To date, however, there have been few attempts at systematically investigating the effects of mechanophore structure upon rates of activation by an acoustic field. Herein, we develop a method for comparing the relative reactivities of various cyclobutane mechanophores. Through the synthesis and ultrasonic irradiation of a molecular weight series of poly(methyl acrylate) polymers in which each macromolecule has a single chain-centered mechanophore, we find measurable and statistically significant shifts in molecular weight thresholds for mechanochemical activation that depend on the structure of the mechanophore. We also show that calculations based on the constrained geometries simulate external force method reliably predict the trends in mechanophore reactivity. These straightforward calculations and the experimental methods described herein may be useful in guiding the design and the development of new mechanophores for targeted applications.