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Co(II)-Mediated and microwave assisted coupling between 2,6-diaminopyridine and nitriles. A new synthetic route to N-(6-aminopyridin-2-yl)carboximidamides

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Abstract

The Chinese-lantern-type Co2(O2CBut)4{2,6-(NH2)2C5H3 N}2 complex reacts with RCN (R = Me or Prn) under microwave irradiation (MWI) to give the mononuclear amidine complexes Co(O2CBut)2{H2N(C5H3 N)NHC(R)=NH} (R = Me (4a) or Prn (4c)). Under microwave irradiation, the addition of 2,6-diaminopyridine to acetonitrile in the presence of the pivalate complexes Co2(μ2-OH2)(O2CBut)4(HO2CBut)4 (1) or [Co(OH)n(O2CBut)2−n ]x (2) afforded complex 4a in higher yield compared to the corresponding reaction performed earlier without MWI. The use of MWI makes it possible to perform analogous reactions with nitriles RCN (R = Et, Prn, or Ph) giving rise to complexes 4b—d, respectively. Compounds 4a—d were characterized by elemental analysis and IR spectroscopy. The structure of complex 4c was established by X-ray diffraction. Amidines H2N(C5H3N)NHC(R)=NH, which formed in the coordination sphere of cobalt(II), were isolated in the free state from methanolic solutions of complexes 4a—d under the action of Na2S and were characterized by electrospray mass spectrometry and 1H and 13C{1H} NMR spectroscopy. The reactions of 2-aminopyridine with both complexes 1 and 2 in acetonitrile under microwave irradiation produced the Co(O2CBut)2(H2NC5H4N)2 complex.

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Authors and Affiliations

  1. Department of Chemistry, St. Petersburg State University, 26 Universitetsky prosp., 198504, Stary Petergof, Russian Federation

    N. A. Bokach & V. Yu. Kukushkin

  2. Department of Chemistry, University of Joensuu, P.O. Box 111, Joensuu, FIN-8010, Finland

    M. Haukka

  3. N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991, Moscow, Russian Federation

    T. B. Mikhailova, A. A. Sidorov & I. L. Eremenko

Authors
  1. N. A. Bokach
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  2. V. Yu. Kukushkin
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  3. M. Haukka
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  4. T. B. Mikhailova
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  5. A. A. Sidorov
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  6. I. L. Eremenko
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 35–42, January, 2006.

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Bokach, N.A., Kukushkin, V.Y., Haukka, M. et al. Co(II)-Mediated and microwave assisted coupling between 2,6-diaminopyridine and nitriles. A new synthetic route to N-(6-aminopyridin-2-yl)carboximidamides. Russ Chem Bull 55, 36–43 (2006). https://doi.org/10.1007/s11172-006-0212-4

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  • DOI: https://doi.org/10.1007/s11172-006-0212-4

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