tert-butyl 4-n-butyl-3,5-dimethylpyrrole-2-carboxylate | 872452-69-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: tert-butyl 4-n-butyl-3,5-dimethylpyrrole-2-carboxylate
• 英文别名: tert-butyl 4-butyl-3,5-dimethylpyrrole-2-carboxylate
• CAS: 872452-69-2
• 化学式: C₁₅H₂₅NO₂
• 分子量: 251.369
• InChiKey: HUMHIGNLOVCMRZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.93
• 重原子数：
  18.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  42.09
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  tert-butyl 4-n-butyl-3,5-dimethylpyrrole-2-carboxylate 在 乙酸酐 、 溶剂黄146 、 三氟乙酸 作用下， 以 异丙醇 为溶剂， 反应 8.17h， 生成 12⁴,13⁴-diaza-8,17-dibutyl-7,18-dimethylacenaphtho[1,2-b]phenanthro[9,10-l]porphyrin
  参考文献：
  名称：

  Porphyrins with exocyclic rings. Part 19: Efficient syntheses of phenanthrolinoporphyrins

  摘要：

  5-Nitro-1,10-phenanthrolines react with isocyanoacetate esters in the presence of DBU in THF to give excellent yields of the corresponding phenanthrolinopyrroles. These were condensed with acetoxymethylpyrroles using catalytic quantities Of p-tolenesulfonic acid in acetic acid to give dipyrrylmethanes, but these structures proved to be poorly suited for porphyrin synthesis due to the electron-withdrawing nature of the fused phenanthroline unit. However, phenanthrolinopyrrole ethyl esters could be converted to the corresponding alpha-unsubstituted pyrroles with KOH in ethylene glycol at 180-190 degrees C and these condensed with 2 equiv of acetoxymethylpyrroles in refluxing acetic acid-isopropyl alcohol to give tripyrranes. In a one pot procedure, tripyrrane di-tert-butyl esters were treated with TFA at room temperature to cleave the protective groups, diluted with dichloromethane, reacted with pyrrole dialdehydes and oxidized to afford phenanthrolinoporphyrins in 52-83% yield. These conditions also allow the synthesis of porphyrins with additional fused acenaphthylene or phenanthrene rings. Although the UV-vis spectra for these porphyrins are unexceptional, the presence of an external coordination site allows many potential applications to be considered. Porphyrins with two phenanthroline units could not be prepared by the '3 + 11 strategy. Instead, alpha-unsubstituted phenanthrolinopyrroles were reacted with a bis(dimethylaminomethyl)pyrrole in refluxing acetic acid to give moderate yields of the corresponding opp-diphenanthrolinoporphyrins. In one case, a triphenanthrolitioporphyrin and trace amounts of an adj-diphenanthrolinoporphyrin were formed as by-products. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.09.089
• 作为产物：
  描述：

  乙酰乙酸叔丁酯 在 sodium acetate 、 溶剂黄146 、 锌 、 sodium nitrite 作用下， 以 水 为溶剂， 反应 4.0h， 生成 tert-butyl 4-n-butyl-3,5-dimethylpyrrole-2-carboxylate
  参考文献：
  名称：

  Porphyrins with exocyclic rings. Part 19: Efficient syntheses of phenanthrolinoporphyrins

  摘要：

  5-Nitro-1,10-phenanthrolines react with isocyanoacetate esters in the presence of DBU in THF to give excellent yields of the corresponding phenanthrolinopyrroles. These were condensed with acetoxymethylpyrroles using catalytic quantities Of p-tolenesulfonic acid in acetic acid to give dipyrrylmethanes, but these structures proved to be poorly suited for porphyrin synthesis due to the electron-withdrawing nature of the fused phenanthroline unit. However, phenanthrolinopyrrole ethyl esters could be converted to the corresponding alpha-unsubstituted pyrroles with KOH in ethylene glycol at 180-190 degrees C and these condensed with 2 equiv of acetoxymethylpyrroles in refluxing acetic acid-isopropyl alcohol to give tripyrranes. In a one pot procedure, tripyrrane di-tert-butyl esters were treated with TFA at room temperature to cleave the protective groups, diluted with dichloromethane, reacted with pyrrole dialdehydes and oxidized to afford phenanthrolinoporphyrins in 52-83% yield. These conditions also allow the synthesis of porphyrins with additional fused acenaphthylene or phenanthrene rings. Although the UV-vis spectra for these porphyrins are unexceptional, the presence of an external coordination site allows many potential applications to be considered. Porphyrins with two phenanthroline units could not be prepared by the '3 + 11 strategy. Instead, alpha-unsubstituted phenanthrolinopyrroles were reacted with a bis(dimethylaminomethyl)pyrrole in refluxing acetic acid to give moderate yields of the corresponding opp-diphenanthrolinoporphyrins. In one case, a triphenanthrolitioporphyrin and trace amounts of an adj-diphenanthrolinoporphyrin were formed as by-products. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.09.089

文献信息

• Synthesis of Porphyrin Dimers Fused with a Benzene Unit
  作者：Hidemitsu Uno、Ken-ichi Nakamoto、Kenji Kuroki、Akiko Fujimoto、Noboru Ono

  DOI：10.1002/chem.200601644

  日期：2007.7.6

  Bicyclo[2.2.2]octadiene-connected pyrrolo-porphyrins have been prepared by an inverse-type [3+1] porphyrin synthesis of a bicyclo[2.2.2]octadiene-fused dipyrrole with a tripyrrane dicarbaldehyde. Another [3+1] porphyrin synthesis of pyrrole-connected porphyrins with the same or other tripyrrane dicarbaldehydes gave bicyclo[2.2.2]octadiene-bridged diporphyrins, the central metals and/or peripheral substituents

  双环[2.2.2]辛二烯连接的吡咯并卟啉已通过反式[3 + 1]卟啉与三吡喃二卡甲醛的双环[2.2.2]辛二烯稠合的双吡咯合成而制备。吡咯连接的卟啉与相同或其他三吡喃二甲醛的另一种[3 + 1]卟啉合成产生双环[2.2.2]辛二烯桥联的二卟啉，其中心金属和/或外围取代基不同。将双环[2.2.2]辛二烯骨架热分解为苯部分，得到高纯度形式的π系统稠合的卟啉二聚体。