ethyl 4-(2-carbethoxy-4,5-dimethyl-1H-3-pyrrolyl)butanoate | 350252-70-9

• 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 4-(2-carbethoxy-4,5-dimethyl-1H-3-pyrrolyl)butanoate
• 英文别名: 2,3-dimethyl-5-ethoxycarbonyl-1H-pyrrole-4-butyric acid ethyl ester；2,3-Dimethyl-5-(ethoxycarbonyl)-(1h)-pyrrole-4-butyric acid ethyl ester；ethyl 3-(4-ethoxy-4-oxobutyl)-4,5-dimethyl-1H-pyrrole-2-carboxylate
• CAS: 350252-70-9
• 化学式: C₁₅H₂₃NO₄
• 分子量: 281.352
• InChiKey: RKEFASSGSKLCGX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  68.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 4-(2-carbethoxy-4,5-dimethyl-1H-3-pyrrolyl)butanoate 在 lithium hydroxide 、 ammonium cerium(IV) nitrate 作用下， 以 四氢呋喃 、 水 、 溶剂黄146 为溶剂， 反应 6.0h， 生成 4-(2-carbethoxy-5-formyl-4-methyl-1H-3-pyrrolyl)butanoic acid
  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：

  丁二酸单乙酯酰氯 在 sodium acetate 、 锌 作用下， 以 水 、 溶剂黄146 为溶剂， 反应 5.5h， 生成 ethyl 4-(2-carbethoxy-4,5-dimethyl-1H-3-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

文献信息

• Hydrogen-Bonded Dimers in Dipyrrinones and Acyldipyrrinones
  作者：Michael T. Huggins、David A. Lightner

  DOI：10.1007/s007060170131

  日期：2001.2.15

  as determined by analysis of variable temperature 1H NMR data. In contrast, when the 9-acyl group is replaced by formyl or when the acyl group is fixed in a syn orientation to the pyrrole NH, the dipyrrinone is strongly prone to dimerization in CHCl3.

  9-酰基-二吡咯烷酮9-丁酰基-2,3,7,8-四甲基-（10 H ）-二吡喃-1-酮的晶体结构测定 表明存在分子间氢键合的二聚体。然而，在CHCl 3溶液中，颜料是单体的，如通过蒸气压渗透压测量法测定的。在C（8），9酰基dipyrrinone仅表现出弱的倾向，在CHCl形成二聚体缺少的烷基3（ ķ 甲 〜60  中号 -1如通过可变温度的分析测定）1 H NMR数据。相反，当9-酰基被甲酰基取代时或当酰基固定在 合成物中时 在吡咯NH的方向上，二吡啶酮在CHCl 3中强烈倾向于二聚。