Volume 3, Issue 2, April 2015, Pages: 14-17
Received: Feb. 25, 2015;
Accepted: Mar. 9, 2015;
Published: Mar. 15, 2015
Views 4160 Downloads 171
Mitsunori Oda, Department of Chemistry, Faculty of Science, Shinshu University, Matsumoto, Nagano, Japan
Yuko Yamaga, Department of Chemistry, Faculty of Science, Shinshu University, Matsumoto, Nagano, Japan
Yoshimitsu Kumai, Department of Chemistry, Faculty of Science, Shinshu University, Matsumoto, Nagano, Japan
Akira Ohta, Department of Chemistry, Faculty of Science, Shinshu University, Matsumoto, Nagano, Japan
Ryuta Miyatake, Centre for Environmental Conservation and Research Safety, University of Toyama, Gofuku, Toyama, Japan
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.
Synthesis and Properties of 2,6-Bis(1-Azaazulen-2-yl)-Pyridine, Modern Chemistry.
Vol. 3, No. 2,
2015, pp. 14-17.
G. R. Newkome, W. E. Puckett, V. K. Gupta, and G. E. Kiefer, “Cyclometalation of the platinum metals with nitrogen and alkyl, alkenyl, and benzyl carbon donors”, Chem. Rev. 1986, 86, 451–489.
G. van Koten, “Tuning the reactivity of metals held in a rigid ligand environment”, Pure & Appl. Chem. 1989, 61, 1681–1684.
J. T. Singleton, “The uses of pincer complexes in organic synthesis”, Tetrahedron 2003, 59, 1837–1857.
N. Selander and K. J. Szabó, “Catalysis by palladium pincer complexes”, Chem. Rev. 2011, 111, 2048–2076.
F, Kröhnke, “The specific synthesis of pyridines and oligopyridines”, Synthesis 1976, 89, 1–24.
N. Abe and T. Gunji, “The chemistry of azaazulenes”, Heterocycles 2010, 82, 201–248
N. Abe, “Recent progress in the chemistry of azaazulenes”, Recent Res. Devel. Org. & Bioorg. Chem. 2001, 4, 17–48.
M. Kimura, “The chemistry of aza-azulenes”, J. Synth. Org. Chem. Jpn. 1981, 39, 690–700
T. Nishiwaki and N. Abe, “Recent progress in the chemistry of azaazulenes: Synthetic methodology and chemical reactions”, Heterocycles 1981, 15, 547–582
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.
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.
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.
I. Sasaki, J. C. Daran, and G. G. A. Balavoine, “An effective route to polysubstituted symmetric terpyridines”, Synthesis 1999, 815–820.
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.
The value of pKb3 could not be obtained because of its spectral change without isosbestic points in strong acidic media.
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).
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.