dimethyl cyanofumarate | 54797-29-4

• 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 cyanofumarate
• 英文别名: dimethyl (E)-2-cyanobut-2-enedioate
• CAS: 54797-29-4
• 化学式: C₇H₇NO₄
• 分子量: 169.137
• InChiKey: FODBHLMSMZRICS-HWKANZROSA-N

物化性质

• 沸点：
  260.8±30.0 °C(Predicted)
• 密度：
  1.226±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  dimethyl cyanofumarate 在 水 、 zinc(II) chloride 作用下， 以 various solvent(s) 为溶剂， 生成 4-Cyano-3,4-dicarbomethoxybutanal
  参考文献：
  名称：

  Influence of Lewis Acids on the Cycloaddition Reactions of Cyano- and Carbomethoxy-Substituted Olefins

  摘要：

  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.

  DOI：

  10.1021/jo00097a054
• 作为产物：
  描述：

  2-氰基丁二酸二甲酯 生成 dimethyl cyanofumarate
  参考文献：
  名称：

  Reactions of the zwitterions from trisubstituted electron-deficient ethylenes and electron-rich olefins

  摘要：

  DOI：

  10.1021/ja00837a020

文献信息

• 6-alkoxy-3,4-dihydro-2h-pyrans from substituted α,β-unsaturated esters
  作者：H.K. Hall、H.A.A. Rasoul、M. Gillard、M. Abdelkader、P. Nogues、R.C. Sentman

  DOI：10.1016/s0040-4039(00)86901-4

  日期：1982.1

  Cycloaddition reactions of substituted α,β-unsaturated esters with various electronich olefins lead to 6-alkoxy-3,4-dihydro-2H-pyrans.

  取代的α，β-不饱和酯与各种电子烯烃的环加成反应会生成6-烷氧基-3,4-二氢-2H-吡喃。
• 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。
• Cycloaddition reactions of allyliron complexes: synthesis of cyclopentanoid derivatives such as (±)-sarkomycin
  作者：Raymond Baker、Rona B. Keen、Michael D. Morris、Ralph W. Turner

  DOI：10.1039/c39840000987

  日期：——

  A cycloaddition reaction between dimethyl 2-cyanofumarate and (σ-3-methoxyallyl)(η5-cyclopentadineyl)dicarbonyliron has yielded a cyclopentanoid derivative which has been used in a synthesis of sarkomycin; a precursor to brefeldin A has also been prepared from the same intermediate.

  二甲基-2- cyanofumarate和（σ-3-甲氧基烯丙基）（η之间的环加成反应5 -cyclopentadineyl）dicarbonyliron已取得已在sarkomycin的合成中使用过的cyclopentanoid衍生物; 布雷菲德菌素A的前体也已经由相同的中间体制备。
• Transition from concerted to stepwise [2 + 4] cycloaddition reactions of .alpha.,.beta.-unsaturated carboxylic esters
  作者：Anne Buyle Padias、Steven T. Hedrick、H. K. Hall

  DOI：10.1021/jo00169a037

  日期：1983.10
• Spontaneous homopolymerization competes with Diels-Alder cycloaddition of 1-aryl-1,3-butadienes to dienophiles containing a leaving group
  作者：Hester A. Clever、Guangyi Wang、William C. Mollberg、Anne Buyle Padias、H. K. Hall

  DOI：10.1021/jo00051a031

  日期：1992.12

  The competition between Diels-Alder cycloaddition and spontaneous concurrent polymerization was investigated in the reactions of 1-phenyl-1,3-butadiene (1) and 1-p-anisyl-1,3-butadiene (2) with electrophilic olefins. The reactions of 1 and 2 with electrophilic olefins trisubstituted with cyano and/or carbomethoxy groups gave only concerted [4 + 2] cycloaddition products. However, when olefins with a leaving group in the beta-position were allowed to react with 1 and 2, cationic homopolymerization of the 1-arylbutadiene competed with the concerted cycloaddition. More polymer was formed with increased electrophilic character of the olefin and with better leaving groups. Formation of a 2-hexene-1,6-zwitterionic intermediate from the s-trans diene and the olefin, which can undergo elimination of the leaving group, is postulated. The resulting carbocation can then initiate cationic homopolymerization.