dimethyl 2,2-dicyanoethene-1,1-dicarboxylate | 82849-49-8

• 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: dimethyl 2,2-dicyanoethene-1,1-dicarboxylate
• 英文别名: dimethyl (dicyanomethylidene)propanedioathe；2,2-dicyano-ethene-1,1-dicarboxylic acid dimethyl ester；Propanedioic acid, (dicyanomethylene)-, dimethyl ester；dimethyl 2-(dicyanomethylidene)propanedioate
• CAS: 82849-49-8
• 化学式: C₈H₆N₂O₄
• 分子量: 194.147
• InChiKey: MOMVYIYOIUVKEW-UHFFFAOYSA-N

物化性质

• 沸点：
  258.7±40.0 °C(Predicted)
• 密度：
  1.315±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  100
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl 2,2-dicyanoethene-1,1-dicarboxylate 以 乙腈 、 苯 为溶剂， 反应 26.0h， 生成 trans-dimethyl 1-(carbazol-9-yl)-4,4-dicyano-1-butene-3,3-dicarboxylate
  参考文献：
  名称：

  Zwitterionic tetramethylenes as the common intermediates in the cycloaddition and polymerization reactions of N-vinylcarbazole with electrophilic tetrasubstituted ethylenes: a new explanation for charge-transfer initiation

  摘要：

  DOI：

  10.1021/ja00276a037
• 作为产物：
  描述：

  丙二酸二甲酯 在 甲醇 、 溴 、 溶剂黄146 、 β-丙氨酸 作用下， 以 甲苯 为溶剂， 反应 26.0h， 生成 dimethyl 2,2-dicyanoethene-1,1-dicarboxylate
  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

• The mechanism of [2 + 1] and [2 + 2] cycloaddition reactions of 1-phenylseleno-2-(trimethylsilyl)ethene: an isotopic labelling study †
  作者：Shoko Yamazaki、Yuichiro Yanase、Kagetoshi Yamamoto

  DOI：10.1039/a909919k

  日期：——

  The reactions of deuterio-labelled 1-seleno-2-silylethenes with trimethyl 2-phosphonoacrylate 2 and methyl vinyl ketone 4 in the presence of SnCl4 gave deuterio-substituted cyclopropanes with 1,2-silicon migration. The reaction of deuterio-labelled 1-seleno-2-silylethenes with dimethyl 2,2-dicyanoethene-1,1-dicarboxylate 6 in the presence of SnCl4 and ZnBr2 gave deuterium-substituted cyclobutanes without silicon migration. This labelling study strongly confirms the 1,2-silicon migration for [2 + 1] cycloadditions of 1 and non-1,2-silicon migration for the [2 + 2] cycloaddition reactions, respectively.

  标记氘的1-硒-2-硅乙烯与三甲基2-磷酸丙烯酸酯2和甲基乙烯酮4在SnCl4存在下反应，生成了具有1,2-硅迁移的氘取代环丙烷。标记氘的1-硒-2-硅乙烯与二甲基2,2-二氰乙烯-1,1-二羧酸酯6在SnCl4和ZnBr2存在下反应，生成了没有硅迁移的氘取代环丁烷。这项标记研究强烈确认了对于1和[2 + 1]环加成反应的1,2-硅迁移以及对于[2 + 2]环加成反应的非1,2-硅迁移。
• 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。
• a(<i>E</i>)-1-Methoxy-1,3-butadiene and 1,1-Dimethoxy-1,3-butadiene in (4 + 2) Cycloadditions. A Mechanistic Comparison
  作者：Reiner Sustmann、Surajin Tappanchai、Heinz Bandmann

  DOI：10.1021/ja961390l

  日期：1996.1.1

  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).
• 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：——

表征谱图