isoquino[5,6-c]pyrrole | 312273-74-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: isoquino[5,6-c]pyrrole
• 英文别名: 2H-pyrrolo[3,4-f]isoquinoline
• CAS: 312273-74-8
• 化学式: C₁₁H₈N₂
• 分子量: 168.198
• InChiKey: KAEVCDYEZDMIKI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.72
• 重原子数：
  13.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  28.68
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  isoquino[5,6-c]pyrrole 在 三氟乙酸 作用下， 以 二氯甲烷 、 溶剂黄146 、 异丙醇 为溶剂， 反应 20.0h， 生成 7,12,13,18-tetraethyl-8,17-dimethylisoquino[5,6-b]porphyrin
  参考文献：
  名称：

  Porphyrins with Exocyclic Rings. 15.¹ Synthesis of Quino- and Isoquinoporphyrins, Aza Analogues of the Naphthoporphyrins

  摘要：

  Porphyrins with fused isoquinoline and quinoline units have been prepared by the "3 +/- 1" methodology. 5-Nitroisoquinoline and 6-nitroquinoline condensed with ethyl isocyanoacetate in the presence of a phosphazene base to give isoquino- and quinopyrroles, respectively. Ester saponification and decarboxylation with KOH in ethylene glycol at 190 degreesC gave the parent azatricycles, and these were further condensed with 2 equiv of an acetoxymethylpyrrole to give the corresponding tripyrranes protected at the terminal positions as their tert-butyl esters. In a one-pot procedure, the ester protective groups were cleaved with TFA, and following dilution with dichloromethane, "3 + 1" condensation with a pyrrole dialdehyde and dehydrogenation of the phlorin intermediate with DDQ gave the targeted azanaphthoporphyrins in excellent yields. Although the UV-vis spectra of these new porphyrin systems are unexceptional, they show promise for further functionalization and applications in the development of porphyrin arrays. In addition, a zinc chelate of the isoquinoporphyrin system shows a high degree of regioselective intermolecular interaction/aggregation in chloroform solution that may lead to selectivity in molecular recognition studies.

  DOI：

  10.1021/jo001216m
• 作为产物：
  描述：

  ethyl isoquino[5,6-c]pyrrole-3-carboxylate 在 氢氧化钾 、 肼 作用下， 以 乙二醇 为溶剂， 反应 0.5h， 以83%的产率得到isoquino[5,6-c]pyrrole
  参考文献：
  名称：

  Porphyrins with Exocyclic Rings. 15.¹ Synthesis of Quino- and Isoquinoporphyrins, Aza Analogues of the Naphthoporphyrins

  摘要：

  Porphyrins with fused isoquinoline and quinoline units have been prepared by the "3 +/- 1" methodology. 5-Nitroisoquinoline and 6-nitroquinoline condensed with ethyl isocyanoacetate in the presence of a phosphazene base to give isoquino- and quinopyrroles, respectively. Ester saponification and decarboxylation with KOH in ethylene glycol at 190 degreesC gave the parent azatricycles, and these were further condensed with 2 equiv of an acetoxymethylpyrrole to give the corresponding tripyrranes protected at the terminal positions as their tert-butyl esters. In a one-pot procedure, the ester protective groups were cleaved with TFA, and following dilution with dichloromethane, "3 + 1" condensation with a pyrrole dialdehyde and dehydrogenation of the phlorin intermediate with DDQ gave the targeted azanaphthoporphyrins in excellent yields. Although the UV-vis spectra of these new porphyrin systems are unexceptional, they show promise for further functionalization and applications in the development of porphyrin arrays. In addition, a zinc chelate of the isoquinoporphyrin system shows a high degree of regioselective intermolecular interaction/aggregation in chloroform solution that may lead to selectivity in molecular recognition studies.

  DOI：

  10.1021/jo001216m

文献信息

• Ruthenium(II) Polypyridyl Complexes Coordinated Directly to the Pyrrole Backbone of π-Extended Boron Dipyrromethene (Bodipy) Dyes: Synthesis, Characterization, and Spectroscopic and Electrochemical Properties
  作者：Shawn Swavey、Sreedhar V. Kumar、Jeremy Erb

  DOI：10.1021/acs.inorgchem.7b01630

  日期：2017.9.5

  A series of new Bodipy dyes incorporating the π-extended isoquino[5,6-c]pyrrole have been synthesized and characterized. The dyes display intense Bodipy (π–π*) transitions and emissions with high quantum efficiencies. Spectroscopic, electrochemical, and theoretical calculations are used to give insight into the frontier orbitals. Coordination of Ru(bpy)2Cl}+ subunits to the peripheral isoquinol nitrogen

  合成并表征了一系列新的Bodipy染料，它们掺入了π扩展的异喹啉[5,6- c ]吡咯。染料显示出强烈的Bodipy（π–π *）跃迁和高量子效率的发射。光谱，电化学和理论计算可用于深入了解前沿轨道。Ru（bpy）2 Cl}的配位+Bodipy染料的外围异喹啉氮原子的亚基会导致三个新的bis-Ru（II）-polypyridyl-Bodipy配合物，其Ru（II）中心直接与二吡啶核核心接触。配合物的光谱研究揭示了与Ru（dπ）到bpy（π*）跃迁相关的传统金属到配体的电荷转移（MLCT）跃迁。但是，在600 nm以上也观察到了更强烈的跃迁。这个过渡是独立的的内消旋的dipyrrin的-取代基和被移位多达25纳米相比，在BODIPY染料没有钌（II）的亚单元，以降低能量。光谱，电化学和光谱电化学研究表明，通过Ru（II）部分的配位，Bodipyπ-轨道不稳定。全部三个茹2–单线态氧络合物显示出在光动力疗法窗口（600–850
• Bichromophoric Properties of Ruthenium(II) Polypyridyl Complexes Bridged by Boron Dipyrromethenes: Synthesis, Electrochemical, Spectroscopic, Computational Evaluation, and Plasmid DNA Photoreactions
  作者：Shawn Swavey、Ashlee Wertz、Jeremy Erb

  DOI：10.1002/ejic.201900527

  日期：2019.8.31

  the typical spectra associated with RuII‐phenanthroline complexes in addition an intense absorption at 618 nm from ππ* transition of the BDP‐core. The spectroscopic properties of this complex were correlated to density functional theory (DFT) and time‐dependent density functional theory (TDDFT) theoretical calculations. This complex shows interesting dual emission of both the Ru(bpy)2phen and the BDP‐core

  以三氟乙酸（TFA）为催化剂，通过无溶剂反应合成了两种新的含异喹啉吡咯和菲并稠合吡咯的π-延伸二吡啶。异喹啉吡咯的硼联吡啶（BDP）是通过标准程序合成的，然后是双钌（II）BDP类似物的合成。研究了该络合物的光谱性质，显示了典型的配体内部电荷转移跃迁（ILCT）以及Ru（dπ）到配体（π*）金属到配体的电荷转移（MLCT）跃迁。观察到在608 nm处发生了强烈的跃迁，摩尔吸收率大于100,000 m –1  cm –1，与BDP核的ππ*跃迁有关。不稳定的bis-Ru II还合成了来自邻菲融合二吡啶的BDP配合物，给出了与Ru II-菲咯啉配合物相关的典型光谱，此外还从BDP核的ππ*跃迁在618 nm处产生了强烈吸收。该复合物的光谱性质与密度泛函理论（DFT）和时变密度泛函理论（TDDFT）理论计算相关。当在453 nm处激发较低能量的MLCT跃迁时，该复合物显示出有趣的Ru（bpy）2
• Evaluation of Endoplasmic Reticulum Targeting Isoquinol‐Based BODIPY Dyes and Their Properties as Molecular Rotors
  作者：Shawn Swavey、David Heidary、Emma Boyd、Jeremy Erb

  DOI：10.1002/ejoc.202300777

  日期：2023.12.13

  A series of six new isoquinol‐based BODIPY dyes have been synthesized by a two‐step method. Unlike traditional synthetic methods, synthesis did not require the use of oxidizing agents or solvent. Spectroscopic, electrochemical and DFT calculations indicate that the properties associated with the six dyes are very similar with little influence of the meso‐substituents. Viscosity studies identified three of the new dyes having properties of molecular rotors for applications in the detection of changes in cellular viscosity. Incubation of the dyes with the HEK cell line show no toxicity up to 10 μM over a 72 h. period. The dyes show the ability to localize within the endoplasmic reticulum (ER) of cells. With two of the dyes showing favorable comparisons to commercially available ER dyes.

  摘要 采用两步法合成了一系列六种新的异喹啉基 BODIPY 染料。与传统合成方法不同，该方法无需使用氧化剂或溶剂。光谱、电化学和 DFT 计算表明，六种染料的相关特性非常相似，中间取代基的影响很小。粘度研究发现，其中三种新染料具有分子转子的特性，可用于检测细胞粘度的变化。将这些染料与 HEK 细胞系一起培养 72 小时，结果表明在 10 μM 以下无毒性。染料显示出在细胞内质网（ER）中定位的能力。其中两种染料与市售的ER染料相比表现良好。
• Photoreactions of DNA with a bimetallic ruthenium(II) polypyridyl complex bridged by an organic chromophore
  作者：Shawn Swavey、Mengyu Wang、Nathaniel Lundy、Jamie Allen

  DOI：10.1016/j.ica.2016.05.033

  日期：2017.1

  A solvent-free reaction of isoquinopyrrole with 3-methoxy-4-hydroxybenzaldehyde results in a new organic chromophore with two peripheral nitrogen coordination sites capable of metal interaction. Reaction of this new chromophore with a ruthenium(II) polypyridyl complex gives a bimetallic complex with rich spectroscopic and electrochemical properties. The new bimetallic complex shows the ability to initiate double strand breaks in plasmid DNA when irradiated with low energy light. (C) 2016 Elsevier B.V. All rights reserved.
• Synthesis, spectroscopic, and electrochemical studies of bis-ruthenium(II) polypyridyl complexes bridged by dipyrromethenes
  作者：Shawn Swavey、David Ireland、Emily Irwin、Jacob Counts

  DOI：10.1016/j.ica.2016.03.008

  日期：2017.1

  By combining substituted aromatic aldehydes and isoquinopyrrole in a reaction flask and heating the reactants in the absence of solvent two new dipyrromethenes have been prepared. The resulting dipyrromethenes show intense absorption bands in the visible region of the spectrum. Ruthenium(II) polypyridyl groups were coordinated to the peripheral nitrogens of the dipyrromethenes to give bimetallic ruthenium(II) complexes in good yield. The ruthenium complexes display interesting spectral properties in the visible region of the spectrum with overlapping intra-ligand (ILCT) and metal-to-ligand (MLCT) charge transfer transitions. Bulk oxidation of the ruthenium(II) centers show a decrease in the MLCT and a shift to lower energy of the ILCT. These complexes may have potential solar cell or theranostic applications. (C) 2016 Elsevier B.V. All rights reserved.