1,2-Dicarbomethoxy-1,2-dicyano-3-(phenylthio)cyclobutane

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1,2-Dicarbomethoxy-1,2-dicyano-3-(phenylthio)cyclobutane
• 英文别名: dimethyl (1R,2S)-1,2-dicyano-3-phenylsulfanylcyclobutane-1,2-dicarboxylate
• 化学式: C₁₆H₁₄N₂O₄S
• 分子量: 330.364
• InChiKey: PZOLJDRYLUUXDR-AGIABQAESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  126
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  dimethyl 2,3-dicyanofumarate 、 苯基乙烯基硫醚 以 1,2-二氯乙烷 为溶剂， 生成 Methyl 4,5-dicyano-6-methoxy-2-phenylsulfanyl-2,3-dihydropyran-4-carboxylate 、 1,2-Dicarbomethoxy-1,2-dicyano-3-(phenylthio)cyclobutane
  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

文献信息

• 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.