phenanthro<9,10-c>pyrrole-1,3-dicarboxaldehyde | 180199-08-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: phenanthro<9,10-c>pyrrole-1,3-dicarboxaldehyde
• 英文别名: 2H-phenanthro[9,10-c]pyrrole-1,3-dicarbaldehyde
• CAS: 180199-08-0
• 化学式: C₁₈H₁₁NO₂
• 分子量: 273.291
• InChiKey: MQRXEBNGCWYVSG-UHFFFAOYSA-N

物化性质

• 熔点：
  >300 °C
• 沸点：
  585.8±35.0 °C(Predicted)
• 密度：
  1.412±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  49.9
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tripyrrane dicarboxylic acid 、 phenanthro<9,10-c>pyrrole-1,3-dicarboxaldehyde 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 3.0h， 以58%的产率得到8,12,13,17-tetraethyl-7,18-dimethylphenanthro[9,10-b]porphyrin
  参考文献：
  名称：

  扩展卟啉发色团：杂卟啉与菲和苊融合

  摘要：

  芳香亚基融合到卟啉发色团上会产生不同的结果，在某些情况下，只观察到轻微的红移。为了扩展这些观察，已经合成了一系列具有稠合苊或菲单元的氧杂、硫杂和硒卟啉。菲[5,6- b]卟啉以前是通过传统的“2+2”麦克唐纳缩合制备的，但现在报道了一种更通用的“3+1”合成。在三氟乙酸存在下，菲并三吡喃与吡咯二醛反应，然后进行氧化步骤，得到苯卟啉。然而，这种化学反应最初产生的产品受到异构体杂质的污染。幸运的是，当反应在相对浓缩的条件下进行时，可以获得良好的异构纯苯卟啉，并且使用这种策略也获得了二苯卟啉。进行了另一种“3+1”合成，其中苯吡咯二醛与三吡喃缩合，这也以良好的产率提供了苯卟啉。呋喃，噻吩和硒吩二醛类似地与菲和苊三吡喃反应，得到一系列具有稠合菲和苊环的杂卟啉。所有这些类卟啉都保留了高度的介电特性。与四吡咯卟啉的情况一样，稠合苊单元的存在导致高度修改的 UV-vis 光谱具有多个 Soret 带和高于

  DOI：

  10.1016/j.tet.2021.132481
• 作为产物：
  描述：

  2H-二苯并[e,g]异吲哚 在 哌啶 、 sodium hydroxide 、 sodium acetate 、 三氯氧磷 作用下， 以 乙醇 、 水 为溶剂， 反应 2.0h， 生成 phenanthro<9,10-c>pyrrole-1,3-dicarboxaldehyde
  参考文献：
  名称：

  ena卟啉的多功能“ 3 +1”合成，一种新的高共轭四吡咯家族

  摘要：

  ena卟啉是一种新的具有强烈红移电子吸收光谱的卟啉，它是通过吡咯-2,5-二甲苯甲醛与并三吡喃酸的酸催化缩合而制得的。同样，通过c-退火的吡咯二醛可得到相关的opp-二萘并卟啉和带有稠合菲和环的混合卟啉体系。

  DOI：

  10.1016/0040-4039(96)00998-7

文献信息

• Synthesis of Sapphyrins, Heterosapphyrins, and Carbasapphyrins by a “4 + 1” Approach
  作者：Daniel T. Richter、Timothy D. Lash

  DOI：10.1021/jo040239o

  日期：2004.12.1

  Sapphyrins are an important group of expanded porphyrins that show valuable anion binding characteristics. In this study, a “4 + 1” route to sapphyrin systems has been developed. Reaction of dialdehydes with a known tetrapyrrole intermediate 11b incorporating a bipyrrolic subunit afforded a wide range of sapphyrin-type products. The best conditions for these reactions involved carrying out the condensation

  鼠尾草素是膨胀的卟啉的重要组，其显示出有价值的阴离子结合特性。在这项研究中，已经开发了一种向沙弗林系统“ 4 +1”的途径。二醛与已知的四吡咯中间体11b的反应掺入双吡咯亚基提供了多种沙弗林类产品。这些反应的最佳条件包括在TFA-二氯甲烷中进行二醛与四吡咯的缩合反应，然后用氯化铁的稀水溶液氧化。吡咯二醛在这些条件下反应以50％的收率得到沙弗林，而呋喃和噻吩二醛以66-90％的收率得到相应的草酸和噻菌红。带有稠合菲或环的吡咯二醛也与11b反应从而以极高的收率得到相关的菲咯啉和啡肽。与卟啉一样，卟啉比相应的菲稠合结构具有更长的波长吸收，尽管差异并不像在卟啉系列中那样明显。11b的反应含1,3-二甲酰基茚的三甲酰基环戊二烯产率为38％，而三甲酰基环戊二烯与四吡咯反应制得的碳青霉烯醛的产率为7-12％。游离碱碳卟啉不稳定，但单质子化的盐酸盐很容易分离和表征。由于存在22π电子离域通路，因此，咔唑啉
• 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.
• Porphyrins with Exocyclic Rings. 13.¹ Synthesis and Spectroscopic Characterization of Highly Modified Porphyrin Chromophores with Fused Acenaphthylene and Benzothiadiazole Rings
  作者：Timothy D. Lash、Pushpa Chandrasekar、Augustine T. Osuma、Sun T. Chaney、John D. Spence

  DOI：10.1021/jo9815655

  日期：1998.11.1

  As part of a survey on the influence of fused aromatic rings on the porphyrin chromophore, a series of novel structures with fused acenaphthylene or benzothiadiazole rings have been synthesized. Base-catalyzed condensation of 1-nitroacenaphthylene or 4-nitrobenzothiadiazole with esters of isocyanoacetic acid afforded good yields of the annelated pyrroles 5 and 28. Cleavage of the ester moieties with KOH in refluxing ethylene glycol gave the unsubstituted heterocycles, and subsequent condensation with 2 equiv of acetoxymethylpyrroles 9 in acetic acid/ethanol produced the modified tripyrranes 12 and 31. Tripyrranes with terminal tert-butyl ester units were treated with TFA and condensed with 3,4-diethyl-2,5-pyrroledicarboxaldehyde 13 in dichloromethane to give, following oxidation with DDQ, the corresponding pi-extended porphyrins 14 and 32. Acenaphthoporphyrins 14 showed unique UV-vis spectra with a triply split Soret band region and a relatively strong band near 660 nm. Strongly red-shifted absorptions were also noted for the dications and the nickel(II), copper(II), and zinc chelates for this system. Thiadiazoloporphyrins 32 gave two broadened Soret bands, but the Q-band region was unexceptional. However, the nickel(II), copper(II), and zinc complexes all showed abnormally strong absorptions between 600 and 612 nm. Porphyrins with two antipodal fused aromatic rings were easily prepared by condensing c-annelated pyrroledialdehydes 17 with tripyrranes 12 and 31, and the spectroscopic properties of the resulting porphyrins showed that the observed ring-fusion effects were essentially additive. Porphyrins with two adjacent acenaphthylene rings were also prepared by the MacDonald "2 + 2" condensation, although this chemistrry gave poor results in the synthesis of a porphyrin with two fused benzothiadiazole rings. The spectroscopic properties of these new highly conjugated porphyrin structures show that ring fusion can profoundly modify the porphyrin chromophore.
• Syntheses of Carbaporphyrinoid Systems Using a Carbatripyrrin Methodology
  作者：Leah M. Stateman、Timothy D. Lash

  DOI：10.1021/acs.orglett.5b02219

  日期：2015.9.18

  A carbatripyrrin intermediate was prepared from commercially available technical-grade indene and 2-pyrrolecarbaldehyde in three steps and 50% overall yield. This novel conjugated structure reacted with pyrroledialdehydes and 2,5-furandicarbaldehyde in the presence of TFA to give good yields of carbaporphyrins and an oxacarbaporphyrin, respectively, and unlike currently available methodologies, no oxidation step was required. The carbatripyrrin also condensed with heterocyclic dicarbinols in the presence of BF3 center dot Et2O to give a series of heterocarbaporphyrins.
• Oxidation with dilute aqueous ferric chloride solutions greatly improves yields in the ‘4+1’ synthesis of sapphyrins
  作者：Daniel T. Richter、Timothy D. Lash

  DOI：10.1016/s0040-4039(99)01352-0

  日期：1999.9

  The use of dilute aqueous FeCl3 as an oxidant, instead of DDQ, greatly improves the yields of sapphyrin products by the '4+1' methodology; yields for carbasapphyrins were somewhat lower but also greatly benefited from this approach. (C) 1999 Elsevier Science Ltd. All rights reserved.