ethyl 3,5-dimethyl-4-[2',2'-dimethyl-1'-(methoxycarbonylmethyl)propyl]-1H-pyrrole-2-carboxylate

• 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 3,5-dimethyl-4-[2',2'-dimethyl-1'-(methoxycarbonylmethyl)propyl]-1H-pyrrole-2-carboxylate
• 化学式: C₁₇H₂₇NO₄
• 分子量: 309.406
• InChiKey: WLJZUXVNVGAJFS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  22.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  68.39
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  3,5-二甲基-1H-吡咯-2-甲酸乙酯 在 氢碘酸 、 亚膦酸 、 乙酸酐 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.42h， 生成 ethyl 3,5-dimethyl-4-[2',2'-dimethyl-1'-(methoxycarbonylmethyl)propyl]-1H-pyrrole-2-carboxylate
  参考文献：
  名称：

  Atropisomerism in monopyrroles

  摘要：

  As observed by NMR, iodopyrroles 1a and 1b (ethyl and methyl 3,5-dimethyl-4-[(1'-iodo-2',2'-dimethyl)propyl]pyrrole-2-carboxylate) and a variety of related derivatives with iodine replaced by methoxy 2, thiomethyl 3, acetic acid esters 4, propionic acid ester 5 or malonic esters 6 exhibit restricted rotation about the C(4)-C(1') bond due to the bulky tert-butyl group and an ortho effect from the sterically crowded 3,5-dimethylpyrrole. Most of the compounds, which are members of the rare class of atropisomers due to restricted rotation about an sp(3)-sp(2) C-C bond, undergo diastereomeric enrichment by preparative TLC and crystallization. From dynamic NMR studies of the enriched diastercomers one can determine kinetic and thermodynamic parameters associated with the atropisomerism, e.g., DeltaG(double dagger) similar to24 kcal/mol for 1 and 5 (313 K), similar to22 kcal/mol for 3 (273 K), and similar to25 kcal/mol for 6 (313 K) in C2D2Cl4 solvent. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00481-0

文献信息

• Atropisomerism in monopyrroles
  作者：Stefan E. Boiadjiev、David A. Lightner

  DOI：10.1016/s0957-4166(02)00481-0

  日期：2002.8

  As observed by NMR, iodopyrroles 1a and 1b (ethyl and methyl 3,5-dimethyl-4-[(1'-iodo-2',2'-dimethyl)propyl]pyrrole-2-carboxylate) and a variety of related derivatives with iodine replaced by methoxy 2, thiomethyl 3, acetic acid esters 4, propionic acid ester 5 or malonic esters 6 exhibit restricted rotation about the C(4)-C(1') bond due to the bulky tert-butyl group and an ortho effect from the sterically crowded 3,5-dimethylpyrrole. Most of the compounds, which are members of the rare class of atropisomers due to restricted rotation about an sp(3)-sp(2) C-C bond, undergo diastereomeric enrichment by preparative TLC and crystallization. From dynamic NMR studies of the enriched diastercomers one can determine kinetic and thermodynamic parameters associated with the atropisomerism, e.g., DeltaG(double dagger) similar to24 kcal/mol for 1 and 5 (313 K), similar to22 kcal/mol for 3 (273 K), and similar to25 kcal/mol for 6 (313 K) in C2D2Cl4 solvent. (C) 2002 Elsevier Science Ltd. All rights reserved.