methyl (E,E)-5-(methylthio)penta-2,4-dienoate | 134360-85-3

• 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: methyl (E,E)-5-(methylthio)penta-2,4-dienoate
• 英文别名: methyl (E,E)- and (E,Z)-5-(methylthio)penta-2,4-dienoate
• CAS: 134360-85-3；134360-98-8
• 化学式: C₇H₁₀O₂S
• 分子量: 158.221
• InChiKey: RUTTZMIDCASVPO-UHMKDZKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.59
• 重原子数：
  10.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  马来酸酐 、 methyl (E,E)-5-(methylthio)penta-2,4-dienoate 以 二氯甲烷 为溶剂， 20.0 ℃ 、1499.99 MPa 条件下， 反应 70.0h， 以98%的产率得到(1R*,2S*,3S*,6R*)-3-(methoxycarbonyl)-6-(methylthio)-4-cyclohexene-1,2-dicarboxylic acid anhydride
  参考文献：
  名称：

  Diels-Alder cycloadditions of electron-rich, electron-deficient, and push-pull dienes with cyclic dienophiles: high-pressure-induced reactions and theoretical calculations

  摘要：

  High-pressure-promoted (4 + 2) cycloadditions of cyclic dienophiles (mainly beta-angelica lactone and cyclopentenone) with electron-rich and push-pull hetero-substituted dienes have been investigated. Only one regio- and stereoisomer was obtained in all cases. While these dienophiles reacted smoothly with alkoxy- and (silyloxy)butadiene derivatives, replacement of oxygen by sulfur resulted in a dramatic decrease in the reactivity of the dienes. On the other hand, push-pull dienes exhibited reactivity similar to that of the electron-rich dienes, in that the dienophilicity was not changed substantially by the influence of an electron-withdrawing group. Theoretical calculations of activation enthalpies have been carried out by the semiempirical AM1 method. These values and frontier orbital considerations have permitted us to interpret the experimental results and to establish a relative order of reactivity of the dienes and dienophiles herein studied.

  DOI：

  10.1021/jo00013a012
• 作为产物：
  描述：

  富马醛酸甲酯 、 (甲硫基甲基)三苯基氯化鏻 在 正丁基锂 作用下， 生成 methyl (E,E)-5-(methylthio)penta-2,4-dienoate
  参考文献：
  名称：

  Diels-Alder cycloadditions of electron-rich, electron-deficient, and push-pull dienes with cyclic dienophiles: high-pressure-induced reactions and theoretical calculations

  摘要：

  High-pressure-promoted (4 + 2) cycloadditions of cyclic dienophiles (mainly beta-angelica lactone and cyclopentenone) with electron-rich and push-pull hetero-substituted dienes have been investigated. Only one regio- and stereoisomer was obtained in all cases. While these dienophiles reacted smoothly with alkoxy- and (silyloxy)butadiene derivatives, replacement of oxygen by sulfur resulted in a dramatic decrease in the reactivity of the dienes. On the other hand, push-pull dienes exhibited reactivity similar to that of the electron-rich dienes, in that the dienophilicity was not changed substantially by the influence of an electron-withdrawing group. Theoretical calculations of activation enthalpies have been carried out by the semiempirical AM1 method. These values and frontier orbital considerations have permitted us to interpret the experimental results and to establish a relative order of reactivity of the dienes and dienophiles herein studied.

  DOI：

  10.1021/jo00013a012