methyl 4-(2-formyl-3-methyl-5-ethynyl-1H-4-pyrrolyl)butanoate | 634606-15-8

• 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: methyl 4-(2-formyl-3-methyl-5-ethynyl-1H-4-pyrrolyl)butanoate
• 英文别名: methyl 4-(2-ethynyl-5-formyl-4-methyl-1H-pyrrol-3-yl)butanoate
• CAS: 634606-15-8
• 化学式: C₁₃H₁₅NO₃
• 分子量: 233.267
• InChiKey: HFFKUYUZNYADGR-UHFFFAOYSA-N

物化性质

• 熔点：
  88-89 °C
• 沸点：
  405.3±45.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  59.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 4-(2-formyl-3-methyl-5-ethynyl-1H-4-pyrrolyl)butanoate 在 bis-triphenylphosphine-palladium(II) chloride 氢氧化钾 、 copper(l) iodide 、 二乙胺 作用下， 以 甲醇 、 水 为溶剂， 反应 63.0h， 生成 bis(2,7-dimethyl-3-ethyl-8-(3-carboxypropyl)dipyrrin-1(10H)-on-8-yl)acetylene
  参考文献：
  名称：

  A New Class of Linear Tetrapyrroles:  Acetylenic 10,10a-Didehydro-10a-homobilirubins

  摘要：

  Novel bilirubin analogues with dipyrrinones conjoined to an acetylene rather than a methylene group were synthesized and examined spectroscopically. Despite the increased separation of the dipyrrinones forced by replacing a -CH2- by a -Cequivalent toC- unit, molecular dynamics calculations show that, like bilirubin, they may still engage in intramolecular hydrogen bonding to carboxylic acid groups when the propionic acid chains are slightly lengthened, e.g., butanoic acids. Unlike bilirubin, however, which is bent in the middle and has a ridge-tile shape, the acetylene orients the attached dipyrrinones along a linear path, and intramolecular hydrogen bonding preserves a twisted linear molecular shape. The extended planes of the dipyrrinones intersect along the -Cequivalent toC- axis at an angle of 136degrees for the conformation stabilized by intramolecular hydrogen bonding in the bis-butyric acid rubin (1b). With shorter acid chains (propionic), only one CO2H can engage an opposing dipyrrinone in intramolecular hydrogen bonding, and in this energy-minimum conformation of the linear pigment la, the intersection of the extended planes of the dipyrrinones has an angle of 171degrees. Spectroscopic evidence for such linearized and twisted structures was found in the pigments' NMR spectral data and their exciton UV-vis and induced circular dichroism spectra.

  DOI：

  10.1021/jo030252t
• 作为产物：
  描述：

  methyl 4-(2-formyl-3-methyl-5-(trimethylsilyl)ethynyl-1H-4-pyrrolyl)butanoate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以85%的产率得到methyl 4-(2-formyl-3-methyl-5-ethynyl-1H-4-pyrrolyl)butanoate
  参考文献：
  名称：

  A New Class of Linear Tetrapyrroles:  Acetylenic 10,10a-Didehydro-10a-homobilirubins

  摘要：

  Novel bilirubin analogues with dipyrrinones conjoined to an acetylene rather than a methylene group were synthesized and examined spectroscopically. Despite the increased separation of the dipyrrinones forced by replacing a -CH2- by a -Cequivalent toC- unit, molecular dynamics calculations show that, like bilirubin, they may still engage in intramolecular hydrogen bonding to carboxylic acid groups when the propionic acid chains are slightly lengthened, e.g., butanoic acids. Unlike bilirubin, however, which is bent in the middle and has a ridge-tile shape, the acetylene orients the attached dipyrrinones along a linear path, and intramolecular hydrogen bonding preserves a twisted linear molecular shape. The extended planes of the dipyrrinones intersect along the -Cequivalent toC- axis at an angle of 136degrees for the conformation stabilized by intramolecular hydrogen bonding in the bis-butyric acid rubin (1b). With shorter acid chains (propionic), only one CO2H can engage an opposing dipyrrinone in intramolecular hydrogen bonding, and in this energy-minimum conformation of the linear pigment la, the intersection of the extended planes of the dipyrrinones has an angle of 171degrees. Spectroscopic evidence for such linearized and twisted structures was found in the pigments' NMR spectral data and their exciton UV-vis and induced circular dichroism spectra.

  DOI：

  10.1021/jo030252t