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Synthesis and Properties of 2,6-Bis(1-Azaazulen-2-yl)-Pyridine

Received: 25 February 2015     Accepted: 9 March 2015     Published: 15 March 2015
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Abstract

The title compound, 2,6-bis(1-azaazulen-2-yl)pyridine (5), was synthesized by condensation between tropone (6) and 2,6-bis(pyridinioacetyl)pyridinium salt (7) in the presence of ammonium acetate. By slow addition of an acetic acid solution of the pyridinium salt 7 to a mixture of 6 and ammonium acetate the yield of 5 was improved. Physical properties of 5 were investigated. It is worthy to note that upon irradiation 5 shows strong emission in acidic media in contrast to very weak emission in neutral media.

Published in Modern Chemistry (Volume 3, Issue 2)
DOI 10.11648/j.mc.20150302.11
Page(s) 14-17
Creative Commons

This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2015. Published by Science Publishing Group

Keywords

Pincer-Type Ligand, Azaazulene, Pyridine, Tropone, Basicity, Emission Behavior

References
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[2] G. van Koten, “Tuning the reactivity of metals held in a rigid ligand environment”, Pure & Appl. Chem. 1989, 61, 1681–1684.
[3] J. T. Singleton, “The uses of pincer complexes in organic synthesis”, Tetrahedron 2003, 59, 1837–1857.
[4] N. Selander and K. J. Szabó, “Catalysis by palladium pincer complexes”, Chem. Rev. 2011, 111, 2048–2076.
[5] F, Kröhnke, “The specific synthesis of pyridines and oligopyridines”, Synthesis 1976, 89, 1–24.
[6] N. Abe and T. Gunji, “The chemistry of azaazulenes”, Heterocycles 2010, 82, 201–248
[7] N. Abe, “Recent progress in the chemistry of azaazulenes”, Recent Res. Devel. Org. & Bioorg. Chem. 2001, 4, 17–48.
[8] M. Kimura, “The chemistry of aza-azulenes”, J. Synth. Org. Chem. Jpn. 1981, 39, 690–700
[9] T. Nishiwaki and N. Abe, “Recent progress in the chemistry of azaazulenes: Synthetic methodology and chemical reactions”, Heterocycles 1981, 15, 547–582
[10] M. Oda, K. Ogura, N. Chung T., S. Kishi, S. Kuroda, K. Fujimori, T. Noda, and N. Abe, “Synthesis and properties of 2-(2-pyridyl)-1-azaazulene”, Tetrahedron Lett. 2007, 48, 4471–4475.
[11] M. Oda, D. Miyawaki, N. Matsumoto, and S. Kuroda, “Palladium-catalyzed amination of 2-chloro-1-azaazulene with 2-aminopyridine”, Heterocycles 2011, 83, 547–554.
[12] M. Oda, A. Sugiyama, R. Takeuchi, Y. Fujiwara, R. Miyatake, T. Abe, and S. Kuroda, “Synthesis, molecular structure, and properties of 2-(2-hydroxyphenyl)-1-azaazulene”, Eur. J. Org. Chem. 2012, 2231–2236.
[13] I. Sasaki, J. C. Daran, and G. G. A. Balavoine, “An effective route to polysubstituted symmetric terpyridines”, Synthesis 1999, 815–820.
[14] Y. Sugimura, N. Soma, and Y. Kishida, “The reaction of troponoid with ylide. III. The reaction of tropone with pyridinium compounds”, Bull. Chem. Soc. Jpn. 1972, 45, 3174–3178.
[15] The value of pKb3 could not be obtained because of its spectral change without isosbestic points in strong acidic media.
[16] Emission quantum yields of 5 in CH3CN and EtOH are less than 1 x 10–3%. The yields were determined by comparison with that of anthracene (0.27 in EtOH).
[17] K. R. Dahnke and L. A. Paquette, “Inverse electron-demand Diels-Alder cycloaddition of a ketene dithioacetal. Copper hydride-promoted reduction of a conjugated enone. 9-Dithiolanobicyclo[3.2.2]non-6-en-2-one from tropone”, Org. Synth. Coll. Vol. 9, 1998, 396–400.
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  • APA Style

    Mitsunori Oda, Yuko Yamaga, Yoshimitsu Kumai, Akira Ohta, Ryuta Miyatake. (2015). Synthesis and Properties of 2,6-Bis(1-Azaazulen-2-yl)-Pyridine. Modern Chemistry, 3(2), 14-17. https://doi.org/10.11648/j.mc.20150302.11

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    ACS Style

    Mitsunori Oda; Yuko Yamaga; Yoshimitsu Kumai; Akira Ohta; Ryuta Miyatake. Synthesis and Properties of 2,6-Bis(1-Azaazulen-2-yl)-Pyridine. Mod. Chem. 2015, 3(2), 14-17. doi: 10.11648/j.mc.20150302.11

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    AMA Style

    Mitsunori Oda, Yuko Yamaga, Yoshimitsu Kumai, Akira Ohta, Ryuta Miyatake. Synthesis and Properties of 2,6-Bis(1-Azaazulen-2-yl)-Pyridine. Mod Chem. 2015;3(2):14-17. doi: 10.11648/j.mc.20150302.11

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  • @article{10.11648/j.mc.20150302.11,
      author = {Mitsunori Oda and Yuko Yamaga and Yoshimitsu Kumai and Akira Ohta and Ryuta Miyatake},
      title = {Synthesis and Properties of 2,6-Bis(1-Azaazulen-2-yl)-Pyridine},
      journal = {Modern Chemistry},
      volume = {3},
      number = {2},
      pages = {14-17},
      doi = {10.11648/j.mc.20150302.11},
      url = {https://doi.org/10.11648/j.mc.20150302.11},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.mc.20150302.11},
      abstract = {The title compound, 2,6-bis(1-azaazulen-2-yl)pyridine (5), was synthesized by condensation between tropone (6) and 2,6-bis(pyridinioacetyl)pyridinium salt (7) in the presence of ammonium acetate. By slow addition of an acetic acid solution of the pyridinium salt 7 to a mixture of 6 and ammonium acetate the yield of 5 was improved. Physical properties of 5 were investigated. It is worthy to note that upon irradiation 5 shows strong emission in acidic media in contrast to very weak emission in neutral media.},
     year = {2015}
    }
    

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  • TY  - JOUR
    T1  - Synthesis and Properties of 2,6-Bis(1-Azaazulen-2-yl)-Pyridine
    AU  - Mitsunori Oda
    AU  - Yuko Yamaga
    AU  - Yoshimitsu Kumai
    AU  - Akira Ohta
    AU  - Ryuta Miyatake
    Y1  - 2015/03/15
    PY  - 2015
    N1  - https://doi.org/10.11648/j.mc.20150302.11
    DO  - 10.11648/j.mc.20150302.11
    T2  - Modern Chemistry
    JF  - Modern Chemistry
    JO  - Modern Chemistry
    SP  - 14
    EP  - 17
    PB  - Science Publishing Group
    SN  - 2329-180X
    UR  - https://doi.org/10.11648/j.mc.20150302.11
    AB  - The title compound, 2,6-bis(1-azaazulen-2-yl)pyridine (5), was synthesized by condensation between tropone (6) and 2,6-bis(pyridinioacetyl)pyridinium salt (7) in the presence of ammonium acetate. By slow addition of an acetic acid solution of the pyridinium salt 7 to a mixture of 6 and ammonium acetate the yield of 5 was improved. Physical properties of 5 were investigated. It is worthy to note that upon irradiation 5 shows strong emission in acidic media in contrast to very weak emission in neutral media.
    VL  - 3
    IS  - 2
    ER  - 

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Author Information
  • Department of Chemistry, Faculty of Science, Shinshu University, Matsumoto, Nagano, Japan

  • Department of Chemistry, Faculty of Science, Shinshu University, Matsumoto, Nagano, Japan

  • Department of Chemistry, Faculty of Science, Shinshu University, Matsumoto, Nagano, Japan

  • Department of Chemistry, Faculty of Science, Shinshu University, Matsumoto, Nagano, Japan

  • Centre for Environmental Conservation and Research Safety, University of Toyama, Gofuku, Toyama, Japan

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