dimethyl 2-((1E,3E)-5-hydroxypenta-1,3-dien-1-yl)-3-methylmaleate | 1579962-43-8

• 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-((1E,3E)-5-hydroxypenta-1,3-dien-1-yl)-3-methylmaleate
• CAS: 1579962-43-8
• 化学式: C₁₂H₁₆O₅
• 分子量: 240.256
• InChiKey: TZMVVUDKUUJWQD-FOXXCQHISA-N

物化性质

• 沸点：
  384.2±37.0 °C(predicted)
• 密度：
  1.135±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.75
• 重原子数：
  17.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  72.83
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  dimethyl 2-((1E,3E)-5-hydroxypenta-1,3-dien-1-yl)-3-methylmaleate 在 2-iodoxybenzoic acid 、 sodium hydride 作用下， 以 四氢呋喃 、 乙酸乙酯 、 mineral oil 为溶剂， 反应 4.41h， 生成 trimethyl (2Z,4E,6Z,8E)-deca-2,4,6,8-tetraene-2,3,9-tricarboxylate
  参考文献：
  名称：

  Base-Stimulated 1,2-, 1,4-, and 1,6-Eliminations in Suitably Substituted Alkylidenesuccinates Leading to Natural and Unnatural Conjugated Alkenyl(methyl)maleic Anhydrides

  摘要：

  With dimethyl maleate as the starting material, facile stereoselective syntheses of natural and unnatural conjugated alkenyl(methyl)maleic anhydrides have been described. The key reactions were base-endorsed novel 1,2-, 1,4-, and 1,6-eliminations in the corresponding alkylidenesuccinate derivatives. The 1,2-eliminations in cyclic carbonate and sulfite by regioselective abstraction of methine protons with the respective release of CO2 and SO2 provided a conjugated ketone product. The characteristic 1,4- and 1,6-elimination reactions with respective release of acetone and mesylate furnished the corresponding unsaturated alcohols. The obtained allylic alcohols were transformed into conjugated alkenyl(methyl)maleic anhydrides via oxidation followed by a Horner-Wadsworth-Emmons reaction pathway in very good yields. The mechanistic aspects involved in these significant elimination reactions have also been described in brief.

  DOI：

  10.1021/jo402857r
• 作为产物：
  描述：

  在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 0.25h， 以64%的产率得到dimethyl 2-((1E,3E)-5-hydroxypenta-1,3-dien-1-yl)-3-methylmaleate
  参考文献：
  名称：

  Base-Stimulated 1,2-, 1,4-, and 1,6-Eliminations in Suitably Substituted Alkylidenesuccinates Leading to Natural and Unnatural Conjugated Alkenyl(methyl)maleic Anhydrides

  摘要：

  With dimethyl maleate as the starting material, facile stereoselective syntheses of natural and unnatural conjugated alkenyl(methyl)maleic anhydrides have been described. The key reactions were base-endorsed novel 1,2-, 1,4-, and 1,6-eliminations in the corresponding alkylidenesuccinate derivatives. The 1,2-eliminations in cyclic carbonate and sulfite by regioselective abstraction of methine protons with the respective release of CO2 and SO2 provided a conjugated ketone product. The characteristic 1,4- and 1,6-elimination reactions with respective release of acetone and mesylate furnished the corresponding unsaturated alcohols. The obtained allylic alcohols were transformed into conjugated alkenyl(methyl)maleic anhydrides via oxidation followed by a Horner-Wadsworth-Emmons reaction pathway in very good yields. The mechanistic aspects involved in these significant elimination reactions have also been described in brief.

  DOI：

  10.1021/jo402857r