1,3-bis(5-tert-butoxycarbonyl-3-butyl-4-methyl-2-pyrrolylmethyl)-7,8-diazaphenanthro[9,10-c]pyrrole | 172806-02-9

• 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-butyl-4-methyl-2-pyrrolylmethyl)-7,8-diazaphenanthro[9,10-c]pyrrole
• 英文别名: tert-butyl 4-butyl-5-[[3-[[3-butyl-4-methyl-5-[(2-methylpropan-2-yl)oxycarbonyl]-1H-pyrrol-2-yl]methyl]-2H-pyrrolo[3,4-f][1,10]phenanthrolin-1-yl]methyl]-3-methyl-1H-pyrrole-2-carboxylate
• CAS: 172806-02-9
• 化学式: C₄₄H₅₅N₅O₄
• 分子量: 717.952
• InChiKey: NMKGPBXPAQJAHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10
• 重原子数：
  53
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  126
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,4-二乙基-1H-吡咯-2,5-二羧醛 、 1,3-bis(5-tert-butoxycarbonyl-3-butyl-4-methyl-2-pyrrolylmethyl)-7,8-diazaphenanthro[9,10-c]pyrrole 在 三乙胺 、 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 生成 2⁴,3⁴-diaza-7,18-dibutyl-12,13-diethyl-8,17-dimethylphenanthro[9,10-b]porphyrin
  参考文献：
  名称：

  通过“ 3 +1”方法合成卟啉：一种制备具有融合的9,10-菲咯啉亚基的卟啉的高级方法

  摘要：

  带有1,10-菲咯啉亚基稠合的卟啉已通过酸催化菲咯啉取代的三吡喃与2,5-吡咯烷二醛的缩合反应以极高的产率制备。

  DOI：

  10.1016/0040-4039(95)02100-0
• 作为产物：
  描述：

  tert-butyl 4-n-butyl-3,5-dimethylpyrrole-2-carboxylate 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-butyl-4-methyl-2-pyrrolylmethyl)-7,8-diazaphenanthro[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

• Porphyrin synthesis by the “3 + 1” methodology: A superior approach for the preparation of porphyrins with fused 9,10-phenanthroline subunits
  作者：Vanning Lin、Timothy D. Lash

  DOI：10.1016/0040-4039(95)02100-0

  日期：1995.12

  Porphyrins with fused 1,10-phenanthroline subunits have been prepared in exceptionally high yields by the acid catalyzed condensation of phenanthroline substituted tripyrranes with a 2,5-pyrroledicarboxaldehyde.

  带有1,10-菲咯啉亚基稠合的卟啉已通过酸催化菲咯啉取代的三吡喃与2,5-吡咯烷二醛的缩合反应以极高的产率制备。
• Porphyrins with exocyclic rings. Part 24. Synthesis and spectroscopic properties of pyrenoporphyrins, potential building blocks for porphyrin molecular wires
  作者：Virajkumar Gandhi、Michelle L. Thompson、Timothy D. Lash

  DOI：10.1016/j.tet.2010.01.046

  日期：2010.3

  Porphyrins with fused pyrene units have been prepared by ‘2+2’ and ‘3+1’ methodologies. Nitration of 1,2,3,6,7,8-tetrahydropyrene, followed by oxidation with DDQ, gave 4-nitropyrene and this condensed with ethyl isocyanoacetate in the presence of DBU or a phosphazene base to generate a pyrenopyrrole ethyl ester. Ester saponification and decarboxylation with KOH in ethylene glycol at 190 °C gave the

  具有稠合pyr单元的卟啉已通过“ 2 + 2”和“ 3 + 1”方法制备。硝化1,2,3,6,7,8-四氢py，然后用DDQ氧化，得到4-硝基py，在DBU或磷腈碱存在下，将其与异氰基乙酸乙酯缩合，生成吡咯并吡咯乙酯。在190°C下用乙二醇在KOH中进行酯化和脱羧，得到母体吡啶并[4,5- c ]吡咯，并进一步与2当量的乙酰氧基甲基吡咯缩合，得到相应的三吡喃并在叔端被保护。丁酯。在一锅法中，用TFA裂解酯保护基，然后用二氯甲烷稀释，用吡咯二醛'3 + 1'缩合，再用DDQ脱氢，生成的目标卟啉卟啉具有良好的总收率。还从pyrenopyrrole中间体制备的二醛和此反应得到的OPP -dipyrenoporphyrin。吡咯并吡咯乙酯在酸催化剂的存在下与二甲氧基甲烷反应生成二戊基吡咯烷基甲烷，并用于制备adj-使用麦当劳“ 2 + 2”方法提取双肾上腺素。吡咯并吡咯二醛还用于制备具有稠合的an
• Synthesis, Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems
  作者：Tetsuo Okujima、John Mack、Jun Nakamura、Gugu Kubheka、Tebello Nyokong、Hua Zhu、Naoki Komobuchi、Noboru Ono、Hiroko Yamada、Hidemitsu Uno、Nagao Kobayashi

  DOI：10.1002/chem.201602213

  日期：2016.10.4

  A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro‐Diels–Alder reaction of bicyclo[2.2.2]octadiene‐fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time‐dependent DFT calculations are used to identify the reasons for

  通过3 + 1卟啉合成方法和随后的双环[2.2.2]辛二烯稠合前体的Diels-Alder逆反应，制备了一系列与,、菲咯啉和苯并荧蒽多环芳环稠合的卟啉。通过分析圆二色性光谱和时间依赖DFT计算的结果，可以确定在产品Q波段的波长和相对强度中观察到趋势的原因。Michl的周长模型用作解释边界π分子轨道相对能量变化的概念框架。
• 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.