phenanthro<9,10-c>pyrrole-1-carboxaldehyde | 217302-35-7

• 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-carboxaldehyde
• 英文别名: 2-formylphenanthro[9,10-c]pyrrole；1-formylphenanthro[9,10-c]pyrrole；2H-phenanthro[9,10-c]pyrrole-3-carbaldehyde
• CAS: 217302-35-7
• 化学式: C₁₇H₁₁NO
• 分子量: 245.28
• InChiKey: RLAFFJDQOIYTBR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  32.9
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  phenanthro<9,10-c>pyrrole-1-carboxaldehyde 在 哌啶 作用下， 以 乙醇 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  Porphyrins with Exocyclic Rings. 13.¹ Synthesis and Spectroscopic Characterization of Highly Modified Porphyrin Chromophores with Fused Acenaphthylene and Benzothiadiazole Rings

  摘要：

  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.

  DOI：

  10.1021/jo9815655
• 作为产物：
  描述：

  ethyl phenanthro<9,10-c>pyrrole-1-carboxylate 在 氢氧化钾 作用下， 以 乙二醇 为溶剂， 反应 0.5h， 生成 phenanthro<9,10-c>pyrrole-1-carboxaldehyde
  参考文献：
  名称：

  Porphyrins with Exocyclic Rings. 13.¹ Synthesis and Spectroscopic Characterization of Highly Modified Porphyrin Chromophores with Fused Acenaphthylene and Benzothiadiazole Rings

  摘要：

  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.

  DOI：

  10.1021/jo9815655

文献信息

• Annulated bacteriochlorins for near-infrared photophysical studies
  作者：Hikaru Fujita、Haoyu Jing、Michael Krayer、Srinivasarao Allu、Gorre Veeraraghavaiah、Zhiyuan Wu、Jianbing Jiang、James R. Diers、Nikki Cecil M. Magdaong、Amit K. Mandal、Arpita Roy、Dariusz M. Niedzwiedzki、Christine Kirmaier、David F. Bocian、Dewey Holten、Jonathan S. Lindsey

  DOI：10.1039/c9nj01113g

  日期：——

  tetrapyrroles, annulation at the β,meso-, β,β-, and β-meso-β-positions also has enabled wavelength tuning. Here, synthetic bacteriochlorins bearing a gem-dimethyl group in each pyrroline ring have provided the foundation for studies of annulation. Seven new free base bacteriochlorins have been prepared and seven others have been elaborated therefrom. Six distinct routes known among porphyrins were explored

  在光科学中的各种应用中都对在近红外（NIR）光谱区域具有强吸收性的分子感兴趣。Nature的NIR吸收剂是细菌叶绿素，其中含有四氢卟啉发色团，该发色团被附着的辅助色素（包括β，内消旋的杂环）所加重。等环的修饰提供了一种方便的波长调谐方法。在其他四吡咯中，在β，内消旋-，β，β-和β-内消旋-β-位置的环化也使波长调谐成为可能。在这里，带有宝石的合成细菌绿素每个吡咯啉环中的-二甲基基团为环化研究提供了基础。已经制备了七种新的游离碱细菌绿素，并由此制备了另外七种。探索了在卟啉中已知的六种不同的途径。最终，phenaleno的或苯并在β组环，内消旋-sites（即，跨越3,5-和13,15-位置）菌绿素的溶液通过需要两个连续的钯介导的耦合反应中的新路由实现二溴代氯霉素与溴代芳基硼酸。对应的Phen-BC或Benz-BC分别在913或1033 nm处吸收。检查由时间分辨光谱显示150个PS或PS
• Violet-blue emitting 2-(N-alkylimino)pyrrolyl organoboranes: Synthesis, structure and luminescent properties
  作者：Paramasivam Krishnamoorthy、Bruno Ferreira、Clara S.B. Gomes、Diogo Vila-Viçosa、Ana Charas、Jorge Morgado、Maria José Calhorda、António L. Maçanita、Pedro T. Gomes

  DOI：10.1016/j.dyepig.2016.11.017

  日期：2017.5

  led to the new mononuclear boron chelate compounds Ph2B[NC4H3C(H)N-R] (R = Me 11; iPr 12; tBu 13; nOct 14; Cy 15; Adam 16), and Ph2B(NC16H9C(H)N-R) (R = Me 17; Adam 18), respectively. Boron complexes 11–16, containing a simple 2-(N-alkylformimino)pyrrolyl ligand, are violet emitters and showed relatively modest fluorescence quantum efficiencies in solution (10%–16%), whereas complexes 17 and 18, bearing

  2- formylpyrrole（的缩合反应1）或2-formylphenanthro [9,10- Ç ]吡咯（2）与得到相应的2- iminopyrrole配体前体的各种脂肪族胺3 - 10，其在与BPH化学计量反应3，导致了新的单核硼螯合物化合物Ph 2 B [NC 4 H 3 C（H）NR]（R = Me 11 ; i Pr 12 ; t Bu 13 ; n Oct 14 ; Cy 15 ; Adam 16）和Ph2 B（NC 16 H 9 C（H）NR）（R = Me 17 ; Adam 18）。硼络合物11 - 16，含有一个简单的2-（Ñ -alkylformimino）吡咯基配体，是紫色发射器和在溶液显示相对适度的荧光量子效率（10％-16％），而配合物17和18，轴承π扩展2-（N-烷基甲亚氨基）菲[9,10- c吡咯基配体是蓝色的发射体，在THF溶液中的量子效率分别提高
• Boron complexes of aromatic ring fused iminopyrrolyl ligands: synthesis, structure, and luminescence properties
  作者：D. Suresh、Bruno Ferreira、Patrícia S. Lopes、Clara S. B. Gomes、Paramasivam Krishnamoorthy、Ana Charas、Diogo Vila-Viçosa、Jorge Morgado、Maria José Calhorda、António L. Maçanita、Pedro T. Gomes

  DOI：10.1039/c6dt02771g

  日期：——

  which, upon reaction with BPh3 in an appropriate molar ratio, led to the new mono- and diboron chelate compounds Ph2B[NC8H5C(H)N-2,6-Ar] (Ar = 2,6-iPr2C6H39; C6H510), Ph2B[(NC8H5C(H)N)2-1,4-C6H4]BPh211, Ph2B(NC16H9C(H)N-Ar) (Ar = 2,6-iPr2C6H312; C6H513), and Ph2B[(NC16H9C(H)N)2-1,4-C6H4]BPh214, respectively. Boron complexes 12–14, containing a phenanthrene fragment fused to the pyrrolyl C3–C4 bond

  2-甲酰基吲哚（1）或2-甲酰基菲[ 9,10 - c ]吡咯（2）与各种芳族胺的缩合反应得到相应的苯基或菲环稠合的单-/双-亚氨基吡咯配体前体3-8。 ，以适当的摩尔比与BPh 3反应，生成新的单硼和双硼螯合物Ph 2 B [NC 8 H 5 C（H）N -2,6-Ar]（Ar = 2,6-iPr 2 C 6 H 3 9 ; C 6 H 5 10），Ph 2 B [（NC 8 H5 C（H）N） 2 -1,4-C 6 H 4 ] BPh 2 11，Ph 2 B（NC 16 H 9 C（H） N -Ar）（Ar = 2,6-iPr 2 C 6 H 3 12； C 6 H 5 13）和Ph 2 B [（NC 16 H 9 C（H）N） 2 -1,4-C 6 H 4 ] BPh 2 14。硼配合物12-14含有与吡咯基C3–C4键融合的菲片段的溶液在溶液中具有很高的荧光性，量子效率分别为37％
• Versatile “3 + 1” syntheses of acenaphthoporphyrins, a new family of highly conjugated tetrapyrroles
  作者：Pushpa Chandrasekar、Timothy D. Lash

  DOI：10.1016/0040-4039(96)00998-7

  日期：1996.7

  Acenaphthoporphyrins, a new group of porphyrins with strongly red shifted electronic absorption spectra, have been prepared by the acid catalysed condensation of a pyrrole-2,5-dicarboxaldehyde with acenaphthotripyrranes; similarly, c-annelated pyrroledialdehydes afforded the related opp-diacenaphthoporphyrins and a mixed porphyrin system with fused phenanthrene and acenaphthylene rings.

  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。