Ethyl 5-carbethoxy-2-formyl-3-methyl-1h-pyrrole-4-hexanoate | 730971-92-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: Ethyl 5-carbethoxy-2-formyl-3-methyl-1h-pyrrole-4-hexanoate
• 英文别名: ethyl 3-(6-ethoxy-6-oxohexyl)-5-formyl-4-methyl-1H-pyrrole-2-carboxylate
• CAS: 730971-92-3
• 化学式: C₁₇H₂₅NO₅
• 分子量: 323.389
• InChiKey: NCKIVSRROHRLEM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  23
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  85.5
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Ethyl 5-carbethoxy-2-formyl-3-methyl-1h-pyrrole-4-hexanoate 在 氢氧化钾 、 lithium hydroxide 、 碘 、 potassium hydrogencarbonate 、 potassium iodide 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 7.34h， 生成 6-(5-Formyl-2-iodo-4-methyl-1H-pyrrol-3-yl)-hexanoic acid methyl ester
  参考文献：
  名称：

  Novel Linear Tetrapyrroles: Hydrogen Bonding in Diacetylenic Bilirubins

  摘要：

  Bilirubin congeners with dipyrrinones conjoined to a diaceteylene unit (-Cequivalent toC-Cequivalent toC-) rather than to -CH2- were synthesized and examined spectroscopically. This new class of rubrified linear tetrapyrroles cannot easily fold or bend in the middle, but the dipyrrinones can rotate independently about the diacetylene unit. Thus, unlike bilirubin, which is bent in the middle and has a ridge-tile shape, the diacetylene unit orients the attached dipyrrinones along a linear path, and intramolecular hydrogen bonding between the dipyrrinones and opposing carboxylic acids preserves a twisted linear molecular shape when the usual propionic acids are replaced by hexanoic. In a bis-hexanoic acid rubin, the extended planes of the dipyrrinones intersect along the -(Cequivalent toC)(2)- axis at an angle of 102degrees for the conformation stabilized by intramolecular hydrogen bonding. With propionic acid chains, however, neither CO2H can engage an opposing dipyrrinone in intramolecular hydrogen bonding, and the energy-minimum conformation of this linear pigment, shows nearly co-planar dipyrrinones, with an intersection of an angle of similar to180degrees of the extended planes of the dipyrrinones. Spectroscopic evidence for such linearized and twisted (bis-hexanoic) and planar (bis-propionic) structures comes from the pigments' NMR spectral data and their exciton UV-Vis and induced circular dichroism spectra.

  DOI：

  10.1007/s00706-003-0157-3
• 作为产物：
  描述：

  6-(氯甲酸基)己炔羧酸乙酯 在 ammonium cerium(IV) nitrate 、 sodium acetate 、 zinc(II) chloride 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 溶剂黄146 为溶剂， 反应 7.5h， 生成 Ethyl 5-carbethoxy-2-formyl-3-methyl-1h-pyrrole-4-hexanoate
  参考文献：
  名称：

  Novel Linear Tetrapyrroles: Hydrogen Bonding in Diacetylenic Bilirubins

  摘要：

  Bilirubin congeners with dipyrrinones conjoined to a diaceteylene unit (-Cequivalent toC-Cequivalent toC-) rather than to -CH2- were synthesized and examined spectroscopically. This new class of rubrified linear tetrapyrroles cannot easily fold or bend in the middle, but the dipyrrinones can rotate independently about the diacetylene unit. Thus, unlike bilirubin, which is bent in the middle and has a ridge-tile shape, the diacetylene unit orients the attached dipyrrinones along a linear path, and intramolecular hydrogen bonding between the dipyrrinones and opposing carboxylic acids preserves a twisted linear molecular shape when the usual propionic acids are replaced by hexanoic. In a bis-hexanoic acid rubin, the extended planes of the dipyrrinones intersect along the -(Cequivalent toC)(2)- axis at an angle of 102degrees for the conformation stabilized by intramolecular hydrogen bonding. With propionic acid chains, however, neither CO2H can engage an opposing dipyrrinone in intramolecular hydrogen bonding, and the energy-minimum conformation of this linear pigment, shows nearly co-planar dipyrrinones, with an intersection of an angle of similar to180degrees of the extended planes of the dipyrrinones. Spectroscopic evidence for such linearized and twisted (bis-hexanoic) and planar (bis-propionic) structures comes from the pigments' NMR spectral data and their exciton UV-Vis and induced circular dichroism spectra.

  DOI：

  10.1007/s00706-003-0157-3

文献信息

• The gem-dimethyl effect: amphiphilic bilirubins
  作者：Bin Tu、Brahmananda Ghosh、David A. Lightner

  DOI：10.1016/j.tet.2004.08.005

  日期：2004.10

  amphiphilicity relative to the parent mesobilirubins without the gem-dimethyls and have highly favorable solubility in organic solvents ranging from nonpolar (benzene) to polar (CH3OH). Like the parent rubins, 1a–1d can easily bend about the middle but unlike the parents they cannot form mesobiliverdin analogs. NMR spectroscopic analysis and molecular dynamics calculations indicate that, like the parents

  通过在酸催化下将两个相同的二吡啶酮与2,2-二甲氧基丙烷偶合，可以平稳地合成新的胆红素同源物（1a – 1d），其中的中心C（10）CH 2被C（CH 3）2取代。新的黄色颜料的酸链从乙酸（n = 1）到丙酸（n = 2）到丁酸（n = 3）到己酸（n = 5）不等，相对于没有宝石的母体中胆红素而言，它们表现出不同寻常的两亲性-在非极性（苯）至极性（CH 3 OH）的有机溶剂中具有很高的溶解度。像父母的红宝石一样，1a– 1d容易在中间弯曲，但与父母不同，它们不能形成mesobiliverdin类似物。NMR光谱分析和分子动力学计算表明，与母体一样，1a - 1d采用通过分子内氢键稳定的脊-瓦形状。1b中构象的确认来自其X射线晶体学结构。