ACS Publications. Most Trusted. Most Cited. Most Read

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Org. Chem. 1998, 63, 8, 2646-2655
RETURN TO ISSUEPREVArticleNEXT

Revised Structures of N-Substituted Dibrominated Pyrrole Derivatives and Their Polymeric Products. Termaleimide Models with Low Optical Band Gaps

View Author Information
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208
Cite this: J. Org. Chem. 1998, 63, 8, 2646–2655
Publication Date (Web):March 24, 1998
https://doi.org/10.1021/jo9722055
Copyright © 1998 American Chemical Society
Request reuse permissions

    Article Views

    2579

    Altmetric

    -

    Citations

    51
    LEARN ABOUT THESE METRICS
    Read OnlinePDF (259 KB)
    Get e-Alerts
    Supporting Info (2)»
    SUBJECTS:

    Abstract

    This paper describes an unexpected rearrangement/oxidation of N-substituted 2,5-dibromopyrroles upon treatment with HNO3. The bromides migrate from the 2,5-positions to the 3,4-positions with subsequent oxidation at the 2,5-positions to afford N-substituted 3,4-dibromomaleimides; the structure was confirmed by single-crystal X-ray analysis. The maleimides were then polymerized to the poly(N-substituted-3,4-maleimide)s with copper bronze. This constitutes a revision of structure for the monomers and polymers. The propensity for the dibromide migration was further confirmed by treatment of N-benzyl-2,5-dibromopyrrole under nonoxidative acidic conditions (p-TsOH) to afford N-benzyl-3,4-dibromopyrrole; both the starting material and product structures were confirmed by single-crystal X-ray analysis. Several termaleimides were prepared from pyrrole, maleic anhydride, and citraconic anhydride. These trimeric compounds underwent enormous shifts in their optical absorbance maxima (ca. 200 nm) when bases or nucleophilic solvents were added. Therefore, the termaleimides served as excellent models for the polymeric systems that had undergone shifts of 350−400 nm upon treatment with the same additives. Ab initio Hartree−Fock and density functional theory were utilized to assess the minimum conformation of the trimeric system. Both terminal maleimides appear canted 37° relative to the central maleimide unit. As the two end maleimide units were computationally forced into closer proximity, there was a dipolar stabilization that ensued between the two terminal maleimides with the formation of a 1,3-dioxetane. However, it is unlikely that there could be the formation of an isolable 1,3-dioxetane due to the large energy difference between the canted structure and the dioxetane. A significant decrease in the HOMO−LUMO energy of 13 kcal/mol was calculated upon formation of the 1,3-dioxetane, suggesting that nucleophiles likely move the canted structure more toward a planar form via addition to the α,β-unsaturated carbonyl units.

    *

    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

    †

     To whom correspondence regarding crystal structure details should be addressed.

    Supporting Information Available

    ARTICLE SECTIONS
    Jump To

    Detailed crystallographic data for 2d, 4a, and N-benzyl-3,4-dibromopyrrole in addition to 1H NMR or 13C NMR spectra for all new compounds (49 pages). This material is contained in libraries on microfiche, immediately follows this article in the microfilm version of the journal, and can be ordered from the ACS; see any current masthead page for ordering information.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 51 publications.

    1. Ewa Surmiak, Aleksandra Twarda-Clapa, Krzysztof M. Zak, Bogdan Musielak, Marcin D. Tomala, Katarzyna Kubica, Przemyslaw Grudnik, Mariusz Madej, Mateusz Jablonski, Jan Potempa, Justyna Kalinowska-Tluscik, Alexander Dömling, Grzegorz Dubin, and Tad A. Holak . A Unique Mdm2-Binding Mode of the 3-Pyrrolin-2-one- and 2-Furanone-Based Antagonists of the p53-Mdm2 Interaction. ACS Chemical Biology 2016, 11 (12) , 3310-3318. https://doi.org/10.1021/acschembio.6b00596
    2. Mathew P. Robin, Paul Wilson, Anne B. Mabire, Jenny K. Kiviaho, Jeffery E. Raymond, David M. Haddleton, and Rachel K. O’Reilly . Conjugation-Induced Fluorescent Labeling of Proteins and Polymers Using Dithiomaleimides. Journal of the American Chemical Society 2013, 135 (8) , 2875-2878. https://doi.org/10.1021/ja3105494
    3. Mary R. Coan, Paola León-Plata, and Jorge M. Seminario . Ab Initio Analysis of the Interactions of GaN Clusters with Oxygen and Water. The Journal of Physical Chemistry C 2012, 116 (22) , 12079-12092. https://doi.org/10.1021/jp302026n
    4. Edson P. Bellido and Jorge M. Seminario . Graphene-Based Vibronic Devices. The Journal of Physical Chemistry C 2012, 116 (15) , 8409-8416. https://doi.org/10.1021/jp2080429
    5. Alejandro J. Gimenez, J. M. Yáñez-Limón, and Jorge M. Seminario . Paper-Based Photoconductive Infrared Sensor. The Journal of Physical Chemistry C 2011, 115 (38) , 18829-18834. https://doi.org/10.1021/jp206287f
    6. Norma L. Rangel, Alejandro Gimenez, Alexander Sinitskii, and Jorge M. Seminario . Graphene Signal Mixer for Sensing Applications. The Journal of Physical Chemistry C 2011, 115 (24) , 12128-12134. https://doi.org/10.1021/jp202790b
    7. Emelia Awuah and Alfredo Capretta . Development of Methods for the Synthesis of Libraries of Substituted Maleimides and α,β-Unsaturated-γ-butyrolactams. The Journal of Organic Chemistry 2011, 76 (9) , 3122-3130. https://doi.org/10.1021/jo1025805
    8. Emily C. Perez-Angel and Jorge M. Seminario . Ab Initio Analysis and Harmonic Force Fields of Gallium Nitride Nanoclusters. The Journal of Physical Chemistry C 2011, 115 (14) , 6467-6477. https://doi.org/10.1021/jp201004w
    9. Jean-Hugues Mirebeau, Mansour Haddad, Martin Henry-Ellinger, Gérard Jaouen, Julien Louvel and Franck Le Bideau. Rearrangement of 2,5-Bis(silylated)-N-Boc Pyrroles into the Corresponding 2,4-Species. The Journal of Organic Chemistry 2009, 74 (22) , 8890-8892. https://doi.org/10.1021/jo901956a
    10. Joseph A. Letizia, Michael R. Salata, Caitlin M. Tribout, Antonio Facchetti, Mark A. Ratner and Tobin J. Marks. n-Channel Polymers by Design: Optimizing the Interplay of Solubilizing Substituents, Crystal Packing, and Field-Effect Transistor Characteristics in Polymeric Bithiophene-Imide Semiconductors. Journal of the American Chemical Society 2008, 130 (30) , 9679-9694. https://doi.org/10.1021/ja710815a
    11. Albert Padwa,, Stephen M. Lynch,, José M. Mejía-Oneto, and, Hongjun Zhang. Cycloaddition Chemistry of 2-Vinyl-Substituted Indoles and Related Heteroaromatic Systems. The Journal of Organic Chemistry 2005, 70 (6) , 2206-2218. https://doi.org/10.1021/jo047834a
    12. Cristiano Zonta,, Fabrizio Fabris, and, Ottorino De Lucchi. The Pyrrole Approach toward the Synthesis of Fully Functionalized Cup-Shaped Molecules. Organic Letters 2005, 7 (6) , 1003-1006. https://doi.org/10.1021/ol047569f
    13. Rafael Chinchilla,, Carmen Nájera, and, Miguel Yus. Metalated Heterocycles and Their Applications in Synthetic Organic Chemistry. Chemical Reviews 2004, 104 (5) , 2667-2722. https://doi.org/10.1021/cr020101a
    14. Carol Y. Zhang and, James M. Tour. Synthesis of Highly Functionalized Pyrazines by Ortho-Lithiation Reactions. Pyrazine Ladder Polymers. Journal of the American Chemical Society 1999, 121 (38) , 8783-8790. https://doi.org/10.1021/ja991683p
    15. P. Sangeetha, Naiyf S. Alharbi, Aleksandr S. Kazachenko, S. Muthu, R. Rajesh. Spectroscopic analysis of 2-amino-1-naphthalenesulfonic acid, molecular docking, and evaluation of the electronic properties of several solvents. Spectroscopy Letters 2023, 56 (6) , 323-342. https://doi.org/10.1080/00387010.2023.2210208
    16. Navjeet Kaur. Synthesis of thietanes-II. 2023, 147-185. https://doi.org/10.1016/B978-0-443-13259-9.00001-7
    17. Yuya Inaba, Yu Kakibayashi, Yuki Ide, Jenny Pirillo, Yuh Hijikata, Tomoki Yoneda, Yasuhide Inokuma. Strain‐Induced Ring Expansion Reactions of Calix[3]pyrrole‐Related Macrocycles. Chemistry – A European Journal 2022, 28 (17) https://doi.org/10.1002/chem.202200056
    18. Ferenc Faigl, Szilvia Deák, Zoltán Mucsi, Tamás Hergert, László Balázs, Boros Sándor, Barbara Balázs, Tamás Holczbauer, Miklós Nyerges, Béla Mátravölgyi. A novel and convenient method for the preparation of 5-(diphenylmethylene)-1 H -pyrrol-2(5 H )-ones; synthesis and mechanistic study. Tetrahedron 2016, 72 (35) , 5444-5455. https://doi.org/10.1016/j.tet.2016.07.032
    19. . Quantum Roots of Crystals and Solids. 2016, 255-348. https://doi.org/10.1201/b21345-4
    20. Qi-Di Zhong, Sheng-Quan Hu, Hong Yan. Crystal structure of 1-benzyl-4-formyl-1 H -pyrrole-3-carboxamide. Acta Crystallographica Section E Crystallographic Communications 2016, 72 (2) , 133-135. https://doi.org/10.1107/S2056989016000128
    21. Ulrike Pfaff, Marcus Korb, Heinrich Lang. Crystal structure of 3-ferrocenyl-1-phenyl-1 H -pyrrole, [Fe(η 5 -C 5 H 4 c C 4 H 3 N Ph)(η 5 -C 5 H 5 )]. Acta Crystallographica Section E Crystallographic Communications 2016, 72 (1) , 92-95. https://doi.org/10.1107/S2056989015024214
    22. Ke Wang, Zhan-Zhu Liu. Synthesis and cytotoxic activities of a series of novel N -methyl-bisindolylmaleimide amide derivatives. Journal of Asian Natural Products Research 2014, 16 (3) , 296-303. https://doi.org/10.1080/10286020.2013.877452
    23. Marcus Korb, Ulrike Pfaff, Alexander Hildebrandt, Tobias Rüffer, Heinrich Lang. 3,4‐Ferrocenyl‐Functionalized Pyrroles: Synthesis, Structure, and (Spectro)Electrochemical Studies. European Journal of Inorganic Chemistry 2014, 2014 (6) , 1051-1061. https://doi.org/10.1002/ejic.201301423
    24. Karim Salazar-Salinas, Carlos Kubli-Garfias, Jorge M. Seminario. Computational design of a CNT carrier for a high affinity bispecific anti-HER2 antibody based on trastuzumab and pertuzumab Fabs. Journal of Molecular Modeling 2013, 19 (7) , 2797-2810. https://doi.org/10.1007/s00894-012-1638-2
    25. Lourdes Castañeda, Zoë V.F. Wright, Cristina Marculescu, Trang M. Tran, Vijay Chudasama, Antoine Maruani, Elizabeth A. Hull, João P.M. Nunes, Richard J. Fitzmaurice, Mark E.B. Smith, Lyn H. Jones, Stephen Caddick, James R. Baker. A mild synthesis of N-functionalised bromomaleimides, thiomaleimides and bromopyridazinediones. Tetrahedron Letters 2013, 54 (27) , 3493-3495. https://doi.org/10.1016/j.tetlet.2013.04.088
    26. Finian J. Leeper, James M. Kelly. Synthesis of 3,4-Disubstituted Pyrroles. A Review. Organic Preparations and Procedures International 2013, 45 (3) , 171-210. https://doi.org/10.1080/00304948.2013.786590
    27. Kenjiro Onimura, Munetoshi Nakamura, Keisuke Amatsu, Mieko Matsushima, Kazuhiro Yamabuki, Tsutomu Oishi. Asymmetric Coupling Polymerizations of 2,3-Dihalido- N -substituted Maleimide Derivatives in the Presence of Chiral Bisoxazolines. Chemistry Letters 2013, 42 (4) , 366-368. https://doi.org/10.1246/cl.121259
    28. Shitao Wang, Wei Hong, Shendong Ren, Jie Li, Mao Wang, Xike Gao, Hongxiang Li. New ladder-type conjugated polymer with broad absorption, high thermal stability, and low band gap. Journal of Polymer Science Part A: Polymer Chemistry 2012, 50 (20) , 4272-4276. https://doi.org/10.1002/pola.26234
    29. Ke Wang, Zheng Yan, Nan Wang, Zhan Zhu Liu. Synthesis and cytotoxic activities of a series of novel N-methylbisindolylmaleimide amino acid ester conjugates. Chinese Chemical Letters 2012, 23 (4) , 462-465. https://doi.org/10.1016/j.cclet.2012.01.033
    30. Alexander Hildebrandt, Steve W. Lehrich, Dieter Schaarschmidt, Romy Jaeschke, Katja Schreiter, Stefan Spange, Heinrich Lang. Ferrocenyl Maleimides – Synthesis, (Spectro‐)Electrochemistry, and Solvatochromism. European Journal of Inorganic Chemistry 2012, 2012 (7) , 1114-1121. https://doi.org/10.1002/ejic.201101191
    31. Nuria Acero, Miguel F. Braña, Loreto Añorbe, Gema Domínguez, Dolores Muñoz-Mingarro, Francesc Mitjans, Jaume Piulats. Synthesis and biological evaluation of novel indolocarbazoles with anti-angiogenic activity. European Journal of Medicinal Chemistry 2012, 48 , 108-113. https://doi.org/10.1016/j.ejmech.2011.11.040
    32. Ivonne Otero-Navas, Jorge M. Seminario. Molecular electrostatic potentials of DNA base–base pairing and mispairing. Journal of Molecular Modeling 2012, 18 (1) , 91-101. https://doi.org/10.1007/s00894-011-1028-1
    33. Kenjiro Onimura, Mieko Matsushima, Munetoshi Nakamura, Tatsuya Tominaga, Kazuhiro Yamabuki, Tsutomu Oishi. Synthesis and fluorescent properties of model compounds for conjugated polymer containing maleimide units at the main chain. Journal of Polymer Science Part A: Polymer Chemistry 2011, 49 (16) , 3550-3558. https://doi.org/10.1002/pola.24792
    34. Jan Bergman, Tomasz Janosik. Five‐Membered Heterocycles: Pyrrole and Related Systems. 2011, 269-375. https://doi.org/10.1002/9783527637737.ch4
    35. Martin G. Banwell, Matthew T. Jones, David T.J. Loong, David W. Lupton, David M. Pinkerton, Jayanta K. Ray, Anthony C. Willis. A Pd[0]-catalyzed Ullmann cross-coupling/reductive cyclization approach to C-3 mono-alkylated oxindoles and related compounds. Tetrahedron 2010, 66 (47) , 9252-9262. https://doi.org/10.1016/j.tet.2010.09.042
    36. Kenjiro Onimura, Mieko Matsushima, Kazuhiro Yamabuki, Tsutomu Oishi. Synthesis and properties of N-substituted maleimides conjugated with 1,4-phenylene or 2,5-thienylene polymers. Polymer Journal 2010, 42 (4) , 290-297. https://doi.org/10.1038/pj.2009.341
    37. Anna Fryszkowska, Helen Toogood, Michiyo Sakuma, JohnâM. Gardiner, GillâM. Stephens, NigelâS. Scrutton. Asymmetric Reduction of Activated Alkenes by Pentaerythritol Tetranitrate Reductase: Specificity and Control of Stereochemical Outcome by Reaction Optimisation. Advanced Synthesis & Catalysis 2009, 351 (17) , 2976-2990. https://doi.org/10.1002/adsc.200900574
    38. M. L. Keshtov, V. A. Barachevskii, A. A. Dunaev, V. A. Vasnev, G. M. Markova, B. A. Izmailov, M. M. Krayushkin, N. G. Shimkina, A. R. Khokhlov. New conjugated poly(aryleneethynylenes) with main-chain photochromic units. Polymer Science Series B 2009, 51 (9-10) , 335-343. https://doi.org/10.1134/S1560090409090036
    39. Chia-Fu Cheng, Zhen-Chang Lai, Yean-Jang Lee. Total synthesis of (±)-camphorataimides and (±)-himanimides by NaBH4/Ni(OAc)2 or Zn/AcOH stereoselective reduction. Tetrahedron 2008, 64 (19) , 4347-4353. https://doi.org/10.1016/j.tet.2008.02.077
    40. Angelique N.C. Lötter, Rakhi Pathak, Thato S. Sello, Manuel A. Fernandes, Willem A.L. van Otterlo, Charles B. de Koning. Synthesis of the dibenzopyrrocoline alkaloid skeleton: indolo[2,1-a]isoquinolines and related analogues. Tetrahedron 2007, 63 (10) , 2263-2274. https://doi.org/10.1016/j.tet.2006.12.063
    41. Gordon W. Gribble. Chapter 2 Pyrroles. 2007, 37-79. https://doi.org/10.1016/S1460-1567(07)80051-1
    42. S. V. Shorunov, M. M. Krayushkin, F. M. Stoyanovich, M. Irie. A convenient synthesis of 3,4-diaryl(hetaryl)-substituted maleimides and maleic anhydrides. Russian Journal of Organic Chemistry 2006, 42 (10) , 1490-1497. https://doi.org/10.1134/S1070428006100162
    43. Yoshinori Kondo, Takahiro Kasahara. Immobilized Indolylboron as a Key Intermediate for Solid-Phase Synthesis of Bisindole Alkaloid Analogs. HETEROCYCLES 2006, 67 (1) , 95. https://doi.org/10.3987/COM-05-S(T)24
    44. Mathieu Dubernet, Virginie Caubert, Jérôme Guillard, Marie-Claude Viaud-Massuard. Synthesis of substituted bis(heteroaryl)maleimides. Tetrahedron 2005, 61 (19) , 4585-4593. https://doi.org/10.1016/j.tet.2005.03.016
    45. Charles B. de Koning, Joseph P. Michael, Rakhi Pathak, Willem A.L. van Otterlo. The synthesis of indolo- and pyrrolo[2,1- a ]isoquinolines. Tetrahedron Letters 2004, 45 (6) , 1117-1119. https://doi.org/10.1016/j.tetlet.2003.12.020
    46. Michael De Rosa, Manuel Marquez. The use of an electrophile carrier to determine the number of intermediates in the chlorination of 1-methylpyrrole. Tetrahedron 2003, 59 (12) , 2125-2129. https://doi.org/10.1016/S0040-4020(03)00187-X
    47. Chang-Guo Zhan, David A. Dixon. Electronic Excitations in Pyrrole: A Test Case for Determination of Chromophores in the Chromogenic Effects of Neurotoxic Hydrocarbons by Time-Dependent Density Functional Theory and Single-Excitation Configuration Interaction Methods. Journal of Molecular Spectroscopy 2002, 216 (1) , 81-89. https://doi.org/10.1006/jmsp.2002.8622
    48. Miguel F Braña, Loreto Añorbe, Gema Tarrasón, Francesc Mitjans, Jaume Piulats. Synthesis and biological evaluation of novel bisindolylmaleimides that inhibit vascular endothelial cell proliferation. Bioorganic & Medicinal Chemistry Letters 2001, 11 (20) , 2701-2703. https://doi.org/10.1016/S0960-894X(01)00535-2
    49. . Chapter 2 Pyrroles. 2000, 35-71. https://doi.org/10.1016/S1460-1567(00)80006-9
    50. Daniel M. Ketcha. Chapter 5.2 Five Membered Ring Systems: Pyrroles and Benzo Derivatives. 1999, 124-143. https://doi.org/10.1016/S0959-6380(99)80009-9
    51. D.-S. CHOI, S. HUANG, M. HUANG, T. S. BARNARD, R. D. ADAMS, J. M. SEMINARIO, J. M. TOUR. ChemInform Abstract: Revised Structures of N-Substituted Dibrominated Pyrrole Derivatives and Their Polymeric Products. Termaleimide Models with Low Optical Band Gaps.. ChemInform 1998, 29 (33) , no-no. https://doi.org/10.1002/chin.199833040
    Download PDF

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect