4-cyano-4,5-bis(methoxycarbonyl)-3-(p-methoxyphenyl)-cyclohex-1-ene | 145398-07-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-cyano-4,5-bis(methoxycarbonyl)-3-(p-methoxyphenyl)-cyclohex-1-ene
• 英文别名: Dimethyl 1-cyano-6-(4-methoxyphenyl)cyclohex-4-ene-1,2-dicarboxylate；dimethyl 1-cyano-6-(4-methoxyphenyl)cyclohex-4-ene-1,2-dicarboxylate
• CAS: 145398-07-8；145512-18-1
• 化学式: C₁₈H₁₉NO₅
• 分子量: 329.353
• InChiKey: OTUGKCICBLBEAH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  85.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  (E)-1-(buta-1,3-diene-1-yl)-4-methoxybenzene 、 dimethyl cyanofumarate 以 1,2-二氯乙烷 为溶剂， 反应 20.0h， 以77%的产率得到4-cyano-4,5-bis(methoxycarbonyl)-3-(p-methoxyphenyl)-cyclohex-1-ene
  参考文献：
  名称：

  Spontaneous homopolymerization competes with Diels-Alder cycloaddition of 1-aryl-1,3-butadienes to dienophiles containing a leaving group

  摘要：

  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.

  DOI：

  10.1021/jo00051a031

文献信息

• 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.