bis-1,3-(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)acenaphtho<1,2-c>pyrrole | 180199-11-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: bis-1,3-(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)acenaphtho<1,2-c>pyrrole
• 英文别名: bis-1,3-(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)acenaphtho[1,2-c]pyrrole；tert-butyl 4-ethyl-5-[[9-[[3-ethyl-4-methyl-5-[(2-methylpropan-2-yl)oxycarbonyl]-1H-pyrrol-2-yl]methyl]-8H-acenaphthyleno[1,2-c]pyrrol-7-yl]methyl]-3-methyl-1H-pyrrole-2-carboxylate
• CAS: 180199-11-5
• 化学式: C₄₀H₄₇N₃O₄
• 分子量: 633.831
• InChiKey: LPPOEFXZQPORCA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  47
• 可旋转键数：
  12
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  100
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis-1,3-(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)acenaphtho<1,2-c>pyrrole 在 三氟乙酸 作用下， 反应 0.17h， 生成
  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
• 作为产物：
  描述：

  Ethyl acenaphtho<1,2-c>pyrrole-7-carboxylate 在 氢氧化钾 作用下， 以 乙醇 、 乙二醇 、 溶剂黄146 为溶剂， 反应 16.0h， 生成 bis-1,3-(5-tert-butoxycarbonyl-3-ethyl-4-methyl-2-pyrrolylmethyl)acenaphtho<1,2-c>pyrrole
  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

• Conjugated Macrocycles Related to the Porphyrins. 21. Synthesis, Spectroscopy, Electrochemistry, and Structural Characterization of Carbaporphyrins
  作者：Timothy D. Lash、Michael J. Hayes、John D. Spence、Melanie A. Muckey、Gregory M. Ferrence、Lisa F. Szczepura

  DOI：10.1021/jo020267b

  日期：2002.7.1

  albeit in low yields ranging from 5 to 8%. These hybrid bridged annulene structures have porphyrin-like electronic absorption spectra with strong Soret bands near 420 nm and a series of Q-bands through the visible region. The proton NMR spectrum confirms the presence of a strong diamagnetic ring current, and the meso-protons show up at 10 ppm, while the internal CH is shielded to approximately -7 ppm

  麦当劳缩合反应的“ 3 +1”变体已被证明是合成碳卟啉的极佳方法。特别地，在TFA存在下，1，3-二烯二甲醛与三吡喃缩合，在用DDQ氧化后，以优异的产率得到一系列苯并羰基卟啉。三甲酰基环戊二烯也可提供碳卟啉产物，尽管收率低，从5％到8％。这些杂化的桥接环结构具有类似卟啉的电子吸收光谱，在420 nm附近具有很强的Soret带，并且在可见光区有一系列Q带。质子NMR光谱证实存在强反磁性环电流，中质子出现在10 ppm处，而内部CH被屏蔽到大约-7 ppm。碳卟啉用TFA进行可逆的质子化。尽管在中等浓度的TFA存在下观察到质子化物质的混合物，酸的初始添加提供了单阳离子。但是，在存在50％TFA的情况下，会生成C质子化的指示。这些指示剂通过苯并咔唑卟啉的苯并部分重新定位pi脱位途径，因此尽管它们仍然保留了强大的大环电流，但仍代表了桥接的苯并[18]环烯。已经制备了带有稠合和菲环的碳卟啉，前者在紫
• Extended porphyrinoid chromophores: heteroporphyrins fused to phenanthrene and acenaphthylene
  作者：Timothy D. Lash、Patrick J. Rauen

  DOI：10.1016/j.tet.2021.132481

  日期：2021.11

  Fusion of aromatic subunits onto porphyrin chromophores produces variable results and in some cases only minor bathochromic shifts are observed. In order to extend these observations, a series of oxa-, thia- and selenaporphyrins with fused acenaphthylene or phenanthrene units have been synthesized. Phenanthro[5,6-b]porphyrins were previously prepared via conventional ‘2 + 2’ MacDonald condensations

  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
• Synthesis of Chrysoporphyrins and a Related Benzopyrene-Fused System
  作者：Timothy D. Lash、Melissa A. Mathius、Deyaa I. AbuSalim

  DOI：10.1021/acs.joc.2c01859

  日期：2022.12.16

  Reaction of 6-nitrochrysene with ethyl isocyanoacetate in the presence of a non-nucleophilic base gave a c-annulated pyrrole ethyl ester that was used to prepare chrysene-fused tripyrranes and a chrysopyrrole dialdehyde. Chrysene-fused tripyrranes were reacted with a pyrrole dialdehyde, but poor yields of chrysoporphyrins were obtained. However, condensation of the chrysopyrrole dialdehyde with a series

  6-硝基屈与异氰基乙酸乙酯在非亲核碱存在下反应得到c-环化吡咯乙酯，用于制备屈烯稠合三吡喃和金吡咯二醛。将 Chrysene-fused tripyrranes 与吡咯二醛反应，但获得的金卟啉收率很低。然而，金吡咯二醛与一系列三吡喃的缩合提供了优异的金卟啉和苊-金卟啉收率。氯化铁 (III) 介导的二己基菊卟啉的氧化环化提供了一种苯并芘稠合卟啉，它表现出强烈的红移电子吸收光谱。DFT 计算表明，金卟啉和苯并芘稠合卟啉都具有互变异构体，这些互变异构体具有通过卟啉核和稠合多环芳烃 (PAH) 单元的 34π 电子离域途径。c-环化吡咯二醛也与卡巴三吡林缩合，生成 PAH 稠合卡巴卟啉，保留了完全的芳香特性。
• Conjugated Macrocycles Related to the Porphyrins. 12.¹ Oxybenzi- and Oxypyriporphyrins:  Aromaticity and Conjugation in Highly Modified Porphyrinoid Structures
  作者：Timothy D. Lash、Sun T. Chaney、Daniel T. Richter

  DOI：10.1021/jo981872a

  日期：1998.11.1

  The "3 + 1" route for porphyrinoid synthesis is an excellent methodology for preparing aromatic porphyrin analogues with six-membered ring subunits. Condensation of 5-formylsalicylaldehyde with tripyrranes 15, 24, and 25 in the presence of 5% TFA-dichloromethane, followed by neutralization and oxidation with DDQ, afforded a series of semiquinone-containing porphyrinoids 12, 26, and 27 in 35-52% yield. In these novel systems, the macrocycle achieves aromatization by undergoing a keto-enol tautomerization whereby the phenolic subunit is transformed so that the inner three carbon atoms become part of the 18 pi-electron aromatic core, whereas the outer carbons generate an enone unit. The aromatic nature of these "oxybenziporphyrins" is evident from their porphyrin-like electronic spectra and the presence of powerful diamagnetic ring currents in their proton NMR spectra, where the inner CH is shifted upfield to delta = -7 ppm, whereas the external meso-protons appear downfield between 8.8 and 10.3 ppm. The presence of a carbonyl unit is confirmed by IR and proton NMR spectroscopy. Addition of trace amounts of TFA give an aromatic monocation, but further protonation to the dication leads to the loss of macrocyclic aromaticity. Modified tripyrranes 15b, 26, and 27 were used to prepare oxybenziporphyrins with fused benzene, phenanthrene, and acenaphthylene ring systems, the former via a tetrahydrobenzo intermediate; and these compounds showed many of the same characteristics, including aromatic free bases and nonaromatic dications. The ring fusion gave rise to gradual bathochromic shifts from benzo- (23) to phenanthro- (26) to acenaphtho- (27) oxybenziporphyrins, which qualitatively followed the same trends observed for true porphyrins, although the influence of the acenaphthylene ring system was somewhat muted in this series. Condensation of isophthalaldehyde with tripyrrane 15a gave the nonaromatic analogue "benziporphyrin" in 28% yield, and this species was thoroughly characterized and contrasted to oxybenziporphyrin 12a. Reaction of 3-hydroxypyridine-2,6-dicarboxaldehyde with tripyrranes under the "3 + 1" conditions afforded exceptionally high yields of the corresponding azaoxybenziporphyrins (named "oxypyriporphyrins''; 35, 47-49), and these structures also exhibited porphyrinoid aromaticity. For this series, the dications retained their aromatic character as did the related nickel(II), copper(II), and zinc chelates. Ring fusion effects were investigated for the oxypyriporphyrins and their metal complexes, and again the major absorptions shifted to higher wavelength from benzo- to phenanthro- to acenaphthooxypyriporphyrins. However the effect of metalation on the oxypyriporphyrin chromophore differed considerably from the trends seen for metalloporphyrins. These results show that novel aromatic porphyrinoids are easily accessible via the "3 + 1" approach, and this work will facilitate in-depth studies on the chemical and physical properties of these exciting new bridged annulene structures.
• 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.