1,3-bis(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-7,8-diaza-6,9-dimethylphenanthro[9,10-c]pyrrole | 872452-72-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 1,3-bis(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-7,8-diaza-6,9-dimethylphenanthro[9,10-c]pyrrole
• 英文别名: tert-butyl 4-ethyl-5-[[3-[[3-ethyl-4-methyl-5-[(2-methylpropan-2-yl)oxycarbonyl]-1H-pyrrol-2-yl]methyl]-6,9-dimethyl-2H-pyrrolo[3,4-f][1,10]phenanthrolin-1-yl]methyl]-3-methyl-1H-pyrrole-2-carboxylate
• CAS: 872452-72-7
• 化学式: C₄₂H₅₁N₅O₄
• 分子量: 689.898
• InChiKey: YTFSULDUHLPHRX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.37
• 重原子数：
  51.0
• 可旋转键数：
  8.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  125.75
• 氢给体数：
  3.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  1,3-bis(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-7,8-diaza-6,9-dimethylphenanthro[9,10-c]pyrrole 、 3,4-二乙基-1H-吡咯-2,5-二羧醛 在 三氟乙酸 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 3.17h， 以61%的产率得到2⁴,3⁴-diaza-8,12,13,17-tetraethyl-2³,3³,7,18-tetramethylphenanthro[9,10-b]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：

  4-ethyl-3,5-dimethyl-pyrrole-2-carboxylic acid tert-butyl ester 在 乙酸酐 、 溶剂黄146 作用下， 以 异丙醇 为溶剂， 反应 3.0h， 生成 1,3-bis(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)-7,8-diaza-6,9-dimethylphenanthro[9,10-c]pyrrole
  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

• Porphyrins with exocyclic rings. Part 19: Efficient syntheses of phenanthrolinoporphyrins
  作者：Timothy D. Lash、Yanning Lin、Bennett H. Novak、Mihir D. Parikh

  DOI：10.1016/j.tet.2005.09.089

  日期：2005.12

  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.