2H-Dibenzo[e,g]isoindole-1-carboxylic acid tert-butyl ester | 155959-33-4

• 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: 2H-Dibenzo[e,g]isoindole-1-carboxylic acid tert-butyl ester
• 英文别名: tert-butyl 2H-phenanthro[9,10-c]pyrrole-3-carboxylate
• CAS: 155959-33-4
• 化学式: C₂₁H₁₉NO₂
• 分子量: 317.387
• InChiKey: DMRZOLOJDOQKEE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.43
• 重原子数：
  24.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  42.09
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2H-Dibenzo[e,g]isoindole-1-carboxylic acid tert-butyl ester 在 zinc diacetate 、 对甲苯磺酸 、 三氟乙酸 作用下， 以 溶剂黄146 为溶剂， 反应 2.25h， 生成 7,13,17-triethyl-8,12,18-trimethylphenanthro[9,10-b]porphyrin
  参考文献：
  名称：

  Porphyrins with Exocyclic Rings. 11.¹ Synthesis and Characterization of Phenanthroporphyrins, a New Class of Modified Porphyrin Chromophores

  摘要：

  To obtain insights into the factors that influence the electronic spectra of conjugated porphyrin systems, a series of porphyrins with fused phenanthrene subunits have been synthesized. 9-Nitrophenanthrene reacted with esters of isocyanoacetic acid in the presence of DBU in THF to give a series of phenanthro[9,10-c]pyrroles 14 in good to excellent yields, and subsequent acid-catalyzed condensation with various (acetoxymethyl)pyrroles 18 gave six examples of dipyrrylmethanes 17 that incorporate a fused phenanthrene ring. Cleavage of the benzyl esters from 17a by hydrogenolysis over 10% Pd/C gave the corresponding dicarboxylic acid 24 and this condensed with diformyldipyrrylmethanes 22 under modified MacDonald "2 + 2" condensation conditions to afford the monophenanthroporphyrins 19 and 20. Dipyrrylmethanes 17d and 17f with mixed benzyl and tert-butyl ester moieties were converted into the related formyl dipyrrylmethanecarboxylic acids 29, and subsequent head-to-tail self-condensation in the presence of p-toluenesulfonic acid yielded two examples of opp-diphenanthroporphyrins 27. Reaction of phenanthropyrroles 14 with dimethoxymethane and p-toluenesulfonic acid in acetic acid afforded the symmetrical dipyrrylmethanes 31, and following cleavage of the ester moieties and MacDonald condensation with dialdehyde 22b, the adj-diphenanthroporphyrin 30 was isolated in moderate yield. Metal chelates of the mono-, opp-di-, and adj-diphenanthroporphyrin systems were also prepared, and the electronic spectra for these modified porphyrin systems and their nickel(II), copper(II), and zinc complexes were examined. Surprisingly, the UV-vis absorptions were only slightly shifted to higher wavelengths than those for octaalkylporphyrins. Reduction of ethyl ester 14a with lithium aluminum hydride gave an unstable carbinol, and subsequent tetramerization in the presence of BF3 etherate and oxidation with DDQ afforded the tetraphenanthroporphyrin 10. The free base porphyrin was virtually insoluble in organic solvents, but protonation with TFA gave a soluble dication 10H(2)(2+) With a strong Soret band at 482 nn and two weaker absorptions at 615 and 668 nm. The bathochromic shifts for 10H(2)(2+) are far more significant than those observed for the mono- and diphenanthroporphyrin structures, although again somewhat less than might have been expected for this extraordinarily high degree of ring fusion.

  DOI：

  10.1021/jo980043m
• 作为产物：
  描述：

  9-硝基菲 、 异氰基乙酸叔丁酯 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以65%的产率得到2H-Dibenzo[e,g]isoindole-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Synthesis of phenanthropyrroles and phenanthrolinopyrroles from isocyanoacetates: An extension of the barton-zard pyrrole condensation

  摘要：

  9-Nitrophenanthrene (1) and 5-nitro-1,10-phenanthroline (4) condensed with esters of isocyanoacetic acid in the presence of one equivalent of DBU to give the corresponding phenanthropyrroles 2 and phenantholinopyrroles 5, respectively, in excellent yields.

  DOI：

  10.1016/s0040-4039(00)77152-8

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
• New highly conjugated porphyrin chromophores: Synthesis of mono- and diphenanthroporphyrins
  作者：Timothy D. Lash、Bennett H. Novak

  DOI：10.1016/0040-4039(95)00818-w

  日期：1995.6

  Porphyrins with one or two fused phenanthrene subunits have been prepared from phenanthro[9,10-c]pyrroles, which are in turn easily prepared from 9-nitrophenanthrene.
• Synthesis of phenanthropyrroles and phenanthrolinopyrroles from isocyanoacetates: An extension of the barton-zard pyrrole condensation
  作者：Timothy D. Lash、Bennett H. Novak、Yanning Lin

  DOI：10.1016/s0040-4039(00)77152-8

  日期：1994.4

  9-Nitrophenanthrene (1) and 5-nitro-1,10-phenanthroline (4) condensed with esters of isocyanoacetic acid in the presence of one equivalent of DBU to give the corresponding phenanthropyrroles 2 and phenantholinopyrroles 5, respectively, in excellent yields.
• Lash Timothy D., Novak Bennett H., Lin Yanning, Tetrahedron Lett, 35 (1994) N 16, S 2493-2494
  作者：Lash Timothy D., Novak Bennett H., Lin Yanning

  DOI：——

  日期：——
• Porphyrins with Exocyclic Rings. 11.¹ Synthesis and Characterization of Phenanthroporphyrins, a New Class of Modified Porphyrin Chromophores
  作者：Bennett H. Novak、Timothy D. Lash

  DOI：10.1021/jo980043m

  日期：1998.6.1

  To obtain insights into the factors that influence the electronic spectra of conjugated porphyrin systems, a series of porphyrins with fused phenanthrene subunits have been synthesized. 9-Nitrophenanthrene reacted with esters of isocyanoacetic acid in the presence of DBU in THF to give a series of phenanthro[9,10-c]pyrroles 14 in good to excellent yields, and subsequent acid-catalyzed condensation with various (acetoxymethyl)pyrroles 18 gave six examples of dipyrrylmethanes 17 that incorporate a fused phenanthrene ring. Cleavage of the benzyl esters from 17a by hydrogenolysis over 10% Pd/C gave the corresponding dicarboxylic acid 24 and this condensed with diformyldipyrrylmethanes 22 under modified MacDonald "2 + 2" condensation conditions to afford the monophenanthroporphyrins 19 and 20. Dipyrrylmethanes 17d and 17f with mixed benzyl and tert-butyl ester moieties were converted into the related formyl dipyrrylmethanecarboxylic acids 29, and subsequent head-to-tail self-condensation in the presence of p-toluenesulfonic acid yielded two examples of opp-diphenanthroporphyrins 27. Reaction of phenanthropyrroles 14 with dimethoxymethane and p-toluenesulfonic acid in acetic acid afforded the symmetrical dipyrrylmethanes 31, and following cleavage of the ester moieties and MacDonald condensation with dialdehyde 22b, the adj-diphenanthroporphyrin 30 was isolated in moderate yield. Metal chelates of the mono-, opp-di-, and adj-diphenanthroporphyrin systems were also prepared, and the electronic spectra for these modified porphyrin systems and their nickel(II), copper(II), and zinc complexes were examined. Surprisingly, the UV-vis absorptions were only slightly shifted to higher wavelengths than those for octaalkylporphyrins. Reduction of ethyl ester 14a with lithium aluminum hydride gave an unstable carbinol, and subsequent tetramerization in the presence of BF3 etherate and oxidation with DDQ afforded the tetraphenanthroporphyrin 10. The free base porphyrin was virtually insoluble in organic solvents, but protonation with TFA gave a soluble dication 10H(2)(2+) With a strong Soret band at 482 nn and two weaker absorptions at 615 and 668 nm. The bathochromic shifts for 10H(2)(2+) are far more significant than those observed for the mono- and diphenanthroporphyrin structures, although again somewhat less than might have been expected for this extraordinarily high degree of ring fusion.