methyl 3,3-dicyanoacrylate | 82849-50-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 3,3-dicyanoacrylate
• 英文别名: 1,1-dicyano-2-(methoxycarbonyl)ethene；methyl β,β-dicyanoacrylate；Methyl dicyanoacrylate；methyl 3,3-dicyanoprop-2-enoate
• CAS: 82849-50-1
• 化学式: C₆H₄N₂O₂
• 分子量: 136.11
• InChiKey: HFMWKBNTSDRPPP-UHFFFAOYSA-N

物化性质

• 沸点：
  247.6±30.0 °C(Predicted)
• 密度：
  1.223±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  73.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,1-二甲氧基-丁-1,3-二烯 、 methyl 3,3-dicyanoacrylate 以 甲苯 为溶剂， 反应 1.0h， 以83%的产率得到Methyl 6,6-dicyano-5,5-dimethoxycyclohex-3-ene-1-carboxylate
  参考文献：
  名称：

  a(E)-1-Methoxy-1,3-butadiene and 1,1-Dimethoxy-1,3-butadiene in (4 + 2) Cycloadditions. A Mechanistic Comparison

  摘要：

  The reactions of (E)-1-methoxy-1,3-butadiene (1) and 1,1-dimethoxy-1,3-butadiene (2) with a series of dienophiles of increasing electrophilicity are described Stereochemical studies reveal that the cycloadditions of 1 are concerted processes, even for the most electron-deficient olefins dimethyl dicyanofumarate and dimethyl dicyanomaleate. 1,1-Dimethoxy-1,3-butadiene reacts under our conditions (dilute solutions and temperatures less than or equal to 60 degrees C) only with those dienophiles which can give zwitterions out of the antiperiplanar conformation of the diene. Zwitterionic intermediates can be trapped by methanol. In the case of tetracyanoethene the kinetics of decay of an intermediate, interpreted as the zwitterion, can be followed by stopped flow techniques: E(a) = 14.8 +/- 0.2 kcal mol(-1), log A = 11.9 +/- 0.1, Delta H double dagger = 10.8 +/- 0.1 kcal mol(-1), Delta S double dagger = -6.2 +/- 0.1 cal mol(-1) K-1, and Delta G double dagger = 11.40 +/- 0.03 kcal mol(-1).

  DOI：

  10.1021/ja961390l
• 作为产物：
  描述：

  乙醛酸甲酯 、 丙二腈 在 溶剂黄146 、 β-丙氨酸 作用下， 以 苯 为溶剂， 反应 18.0h， 以38%的产率得到methyl 3,3-dicyanoacrylate
  参考文献：
  名称：

  Dimethyl 1,1-dicyanoethene-2,2-dicarboxylate, a new electrophilic olefin

  摘要：

  DOI：

  10.1021/jo00144a033

文献信息

• Cycloadditions of Bifunctional Vinyl Ethers with Electrophilic Alkenes through Tetramethylene Zwitterion Intermediates
  作者：Eric J. May、Anne Buyle Padias、Robert B. Bates、Henry K. Hall

  DOI：10.1002/hlca.200590112

  日期：2005.6

  Bifunctional vinyl ethers react with electron-poor alkenes to cyclobutanes in good yields. The second CC bond reacted with neither the cyclobutane nor its zwitterion intermediate, even on heating. Cyclobutanes formed from ‘tetracyanoethylene’ (8) were transformed into tetrahydropyridines by reaction of the corresponding zwitterion with MeCN as the solvent. In contrast, cyclobutanes formed from dimethyl

  双官能乙烯基醚与贫电子烯烃反应以高收率反应成环丁烷。即使在加热时，第二个CC键也不会与环丁烷或其两性离子中间体反应。通过相应的两性离子与MeCN作为溶剂的反应，将由“四氰基乙烯”（8）形成的环戊二酮转化为四氢吡啶。相反，由二（二氰基亚甲基）丙二酸二甲酯（9）形成的环丁烷不与MeCN反应，这归因于两性离子中间体的稳定性降低和空间效应增加。这些结果扩展了Huisgen及其同事的经典研究。
• Sustmann, Reiner; Siangouri-Feulner, Ioana, Chemische Berichte, 1993, vol. 126, # 5, p. 1241 - 1246
  作者：Sustmann, Reiner、Siangouri-Feulner, Ioana

  DOI：——

  日期：——
• Rese, Michael; Dern, Mechthild; Luecking, Karin, Liebigs Annalen, 1995, # 7, p. 1139 - 1152
  作者：Rese, Michael、Dern, Mechthild、Luecking, Karin、Sustmann, Reiner

  DOI：——

  日期：——
• Sustmann, Reiner; Luecking, Karin; Kopp, Gebhard, Angewandte Chemie, 1989, vol. 101, # 12, p. 1701 - 1704
  作者：Sustmann, Reiner、Luecking, Karin、Kopp, Gebhard、Rese, Michael

  DOI：——

  日期：——
• 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.