methyl 3,5-dimethyl-4-[(1'-iodo-2',2'-dimethyl)propyl]pyrrole-2-carboxylate | 493006-19-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: methyl 3,5-dimethyl-4-[(1'-iodo-2',2'-dimethyl)propyl]pyrrole-2-carboxylate
• 英文别名: methyl 1'-iodo-neopentylpyrrole-2-carboxylate；Methyl 3,5-dimethyl-4-(1'-iodoneopentyl)-1h-pyrrole-2-carboxylate；methyl 4-(1-iodo-2,2-dimethylpropyl)-3,5-dimethyl-1H-pyrrole-2-carboxylate
• CAS: 493006-19-2
• 化学式: C₁₃H₂₀INO₂
• 分子量: 349.212
• InChiKey: UHKXCAIJPRRXPS-UHFFFAOYSA-N

物化性质

• 沸点：
  393.8±42.0 °C(Predicted)
• 密度：
  1.454±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  42.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  丙酸甲酯 、 methyl 3,5-dimethyl-4-[(1'-iodo-2',2'-dimethyl)propyl]pyrrole-2-carboxylate 在 lithium diisopropyl amide 、 六甲基磷酰三胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以95%的产率得到methyl 3,5-dimethyl-4-[2',2'-dimethyl-1'-(1"-methoxycarbonylethyl)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
• 作为产物：
  描述：

  3,5-二甲基-1H-吡咯-2-羧酸甲酯 、 特戊醛 在 氢碘酸 、 亚膦酸 、 乙酸酐 作用下， 反应 0.42h， 以86%的产率得到methyl 3,5-dimethyl-4-[(1'-iodo-2',2'-dimethyl)propyl]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

• Stable Monopyrrole Atropisomers
  作者：Stefan E. Boiadjiev、David A. Lightner

  DOI：10.1007/s00706-002-0512-9

  日期：2002.10.1

  crystallization: the diastereomers are stable in solution at room temperature. A crystal of one of the diastereomers, suitable for X-ray crystallography, gave the relative configuration of the chiral axis and stereogenic center at C(1′). Dynamic NMR studies of the purified diastereomers provide kinetic and thermodynamic parameters associated with the atropisomerism: Δ G ‡ = 132–134 kJ/mol (∼32 kcal/mol)

  乙基和3,5-二甲基-4-（1'-碘戊戊基）-1 H- 吡咯-2-羧酸甲酯的丙二酸酯衍生物 显示出绕吡咯C（4）-C（1'）键的旋转受限庞大的1'- 叔 丁基和丙二酸酯基和在空间拥挤的3,5-二甲基吡咯的C（4）处的 邻位 效应。丙二酸酯属于稀有的阻转异构体，围绕sp 3 –sp 2旋转受限C–C键，它们通过TLC和结晶进行非对映异构分离：非对映异构体在室温下在溶液中稳定。适用于X射线晶体学的非对映异构体之一的晶体给出了C（1'）上手性轴和立体中心的相对构型。纯化的非对映异构体的动态NMR研究提供了与对映异构有关的动力学和热力学参数：  在383 K的C 2 D 2 Cl 4溶剂中， ΔG ‡ = 132–134 kJ / mol（〜32 kcal / mol）。