5-(methoxycarbonyl)-3-methyl-3(E)-pentenoic acid | 146061-20-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子
• 英文名称: 5-(methoxycarbonyl)-3-methyl-3(E)-pentenoic acid
• 英文别名: (E)-6-methoxy-3-methyl-6-oxohex-3-enoic acid
• CAS: 146061-20-3
• 化学式: C₈H₁₂O₄
• 分子量: 172.181
• InChiKey: YGFLLBSCZQXQDL-ZZXKWVIFSA-N

物化性质

• 沸点：
  304.9±22.0 °C(Predicted)
• 密度：
  1.131±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.97
• 重原子数：
  12.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  63.6
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  5-(methoxycarbonyl)-3-methyl-3(E)-pentenoic acid 在 sodium hydroxide 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 N,N,N',3-tetramethyl-3(E)-hexenediamide
  参考文献：
  名称：

  Effects of backbone rigidification on intramolecular hydrogen bonding in a family of diamides

  摘要：

  In an effort to gain insight on the balance of noncovalent forces that controls the adoption of folded conformations in small molecules, we have examined intramolecular hydrogen bond formation in a series of diamides containing a variety of conformational constraints. The intramolecularly hydrogen-bonded state of flexible diamide 2 was previously shown to be enthalpically favored by about 1.5 kcal/mol relative to the non-hydrogen-bonded state in methylene chloride. For flexible diamide 1, however, the enthalpic preference for the intramolecularly hydrogen-bonded state is only about 0.4 kcal/mol in this solvent. We describe here the synthesis and behavior of diamides 3-9, in which eight- or nine-membered-ring N-H...O=C hydrogen bonds occur in rigidified frameworks. Thermodynamic parameters were determined spectroscopically for the two-state equilibrium, non-hydrogen-bonded vs intramolecularly hydrogen-bonded, for diamides 3 and 4 in methylene chloride. The intramolecularly hydrogen-bonded state of 3 is enthalpically favored by ca. 1.6 kcal/mol. The enhanced enthalpic favorability of the internally hydrogen-bonded state of 3, relative to 1, is consistent with the MM2/MacroModel prediction that formation of an optimal hydrogen bond by 1 requires an eclipsed torsion angle in the linking segment. The intramolecularly hydrogen-bonded state of 4 is enthalpically favored by about 1.1 kcal/mol. The diminished enthalpic favorability relative to 3 may result from the poorer hydrogen-bond-accepting ability of the lactam carbonyl, relative to the acyclic tertiary carbonyl of 3. The extent of intramolecular hydrogen bonding in 5 is less than or equal to the extent in 2 at all temperatures in methylene chloride. Among the olefinic series 6-8, the addition of methyl substituents to the alkene carbons is found to promote hydrogen bond formation so effectively that 8 is predominantly hydrogen bonded in acetonitrile at room temperature, conditions under which little or no intramolecular hydrogen bonding can be detected for 1 or 6. X-ray diffraction data show that the intramolecular hydrogen bond is maintained by 8 in the solid state.

  DOI：

  10.1021/ja00056a017
• 作为产物：
  描述：

  6-bromo-4-methyl-3(E)-hexen-1-ol 在 chromium(VI) oxide 、 硫酸 作用下， 以 水 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 49.5h， 生成 5-(methoxycarbonyl)-3-methyl-3(E)-pentenoic acid
  参考文献：
  名称：

  Effects of backbone rigidification on intramolecular hydrogen bonding in a family of diamides

  摘要：

  In an effort to gain insight on the balance of noncovalent forces that controls the adoption of folded conformations in small molecules, we have examined intramolecular hydrogen bond formation in a series of diamides containing a variety of conformational constraints. The intramolecularly hydrogen-bonded state of flexible diamide 2 was previously shown to be enthalpically favored by about 1.5 kcal/mol relative to the non-hydrogen-bonded state in methylene chloride. For flexible diamide 1, however, the enthalpic preference for the intramolecularly hydrogen-bonded state is only about 0.4 kcal/mol in this solvent. We describe here the synthesis and behavior of diamides 3-9, in which eight- or nine-membered-ring N-H...O=C hydrogen bonds occur in rigidified frameworks. Thermodynamic parameters were determined spectroscopically for the two-state equilibrium, non-hydrogen-bonded vs intramolecularly hydrogen-bonded, for diamides 3 and 4 in methylene chloride. The intramolecularly hydrogen-bonded state of 3 is enthalpically favored by ca. 1.6 kcal/mol. The enhanced enthalpic favorability of the internally hydrogen-bonded state of 3, relative to 1, is consistent with the MM2/MacroModel prediction that formation of an optimal hydrogen bond by 1 requires an eclipsed torsion angle in the linking segment. The intramolecularly hydrogen-bonded state of 4 is enthalpically favored by about 1.1 kcal/mol. The diminished enthalpic favorability relative to 3 may result from the poorer hydrogen-bond-accepting ability of the lactam carbonyl, relative to the acyclic tertiary carbonyl of 3. The extent of intramolecular hydrogen bonding in 5 is less than or equal to the extent in 2 at all temperatures in methylene chloride. Among the olefinic series 6-8, the addition of methyl substituents to the alkene carbons is found to promote hydrogen bond formation so effectively that 8 is predominantly hydrogen bonded in acetonitrile at room temperature, conditions under which little or no intramolecular hydrogen bonding can be detected for 1 or 6. X-ray diffraction data show that the intramolecular hydrogen bond is maintained by 8 in the solid state.

  DOI：

  10.1021/ja00056a017