Synthesis and some reactions of 1,2-diamino-1,3-diaza- and 1,2-diamino-1-azaazulenium salts

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Noritaka Abe, Kunihiko Odagiri, Miki Otani, Etsuko Fujinaga, Hiroyuki Fujii and Akikazu Kakehi


Abstract

Amination of azaazulenes 1–3 with O-mesitylsulfonylhydroxylamine occurs at N-1 and gives the corresponding azaazulenium salts 4–6. The treatment of the salts 4 and 6 with potassium carbonate gives 1-amino-2-imino-1,2-dihydro-1,3-diaza- and 1-azaazulenes. The structure of 1-amino-2-ethylimino-1,2-dihydro-1-azaazulene (10) was characterized by X-ray crystal structure analysis. Reaction of the salt 4 with acetic anhydride gave 2-methyl-1,3,3a,9-tetraazacyclopent[a]azulene. The reaction of the salts 4 and 5 with diethyl ethoxymethylenedicarboxylate (DEEM) in the presence of potassium carbonate in acetonitrile gave 1,3,3a,9-tetraaza- (19) and 1,3,3a-triazacyclopent[a]azulene derivatives (21) as major products, whereas the reaction in ethanol gave 1,2a,3-triaza- (17) and 2a,3-diazabenz[cd]azulene derivatives (22), respectively. Similar treatment of 6 with DEEM gave diethyl (2-ethylimino-1,2-dihydro-1-azaazulen-1-yl)aminomethylenemalonate 23, which converted to 2a,3-diazabenz[cd]azulene derivative (24). The salts 4–6 reacted with active methylene compounds such as diethyl acetonedicarboxylate, diethyl oxalacetate and ethyl pyruvate, at the N-amino group followed by a cyclization at the C-8 position on the azaazulene ring to give 1,2a,3-triaza- (25, 28, 29) and 2a,3-diazabenz[cd]azulene derivatives (26, 27, 30). Cycloaddition of the salts 4–6 with acetylenic esters in the presence of potassium carbonate proceeded regioselectively and gave 1,2a,3-triaza- (32–35) or 2a,3-diazabenz[cd]azulene derivatives (31, 36, 37, 39–41).


References

  1. T. Okamoto and M. Hirobe, Yuki Gosei Kagaku Kyokaishi, 1968, 26, 746 Search PubMed; H.-J. Timp, Adv. Heterocycl. Chem., 1974, 17, 213; W. J. McKillop, E. A. Sedor, B. M. Culbertson and S. Wawzonek, Chem. Rev., 1973, 73, 255 CrossRef CAS; C. G. Stuckwisch, Synthesis, 1973, 469 CrossRef CAS; Y. Tamura, J. Minamikawa and M. Ikeda, Synthesis, 1977, 1 CrossRef CAS; Y. Tamura and M. Ikeda, Adv. Heterocycl. Chem., 1981, 29, 71 CAS.
  2. N. Abe, K. Odagiri and A. Kakehi, J. Chem. Soc., Perkin Trans. 1, 1997, 2189 RSC.
  3. (a) T. Okamoto, M. Hirobe, Y. Tamai and E. Yabe, Chem. Pharm. Bull., 1966, 14, 506 CAS; (b) K. T. Potts, H. R. Burton and J. Bhttacharyya, J. Org. Chem., 1966, 31, 260 CAS.
  4. N. V. Baranova, A. K. Sheinkman and A. N. Kost, Khim. Geterotsikl. Soedin, 1973, 1266 Search PubMed.
  5. K. T. Potts, R. Dugas and C. R. Surapaneni, J. Heterocycl. Chem., 1973, 10, 821 CAS.
  6. Y. Tamura, J.-H. Kim, Y. Sumida and M. Ikeda, Yakugaku Zasshi, 1975, 95, 1497 CAS.
  7. N. Nakao and G. Sunagawa, Chem. Pharm. Bull., 1965, 13, 465.
  8. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, Tennessee( 1976) Search PubMed.
  9. MOPAC version 7.01 for Linux (Public domain Softwareversion;..
  10. J. J. P. Stewart, J. Comput. Chem., 1989, 10, 209, 221.
  11. T. Sasaki, K. Kanematsu and A. Kakehi, J. Org. Chem., 1972, 37, 3106 CrossRef CAS.
  12. Y. Tamura, Y. Miki, Y. Sumida and M. Ikeda, J. Chem. Soc., Perkin Trans. 1, 1973, 2580 RSC.
  13. R. Huisgen, R. Grashey and R. Krishke, Tetrahedron Lett., 1962, 387 CrossRef CAS; V. Boekelheide and N. A. Fedoruk, J. Org. Chem., 1968, 33, 2062 CrossRef CAS; Y. Tamura, Y. Miki and M. Ikeda, J. Heterocycl. Chem., 1975, 12, 119 CAS; Y. Tamura, Y. Sumida, Y. Miki and M. Ikeda, J. Chem. Soc., Perkin Trans. 1, 1975, 407 Search PubMed; J. M. Mingues, M. I. Castello, J. J. Vaquero, L. Garcia-Navio, J. Alvarez-Builla, O. Castano and J. L. Andres, J. Org. Chem., 1996, 61, 4655 CrossRef CAS.
  14. C. J. Gilmore, J. Appl. Crystallogr., 1984, 17, 42 CrossRef CAS.
  15. TEXSAN TEXRAY Structure Analysis Package, Molecular Structure Corporation ( 1985).
  16. M. C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, G. Polidoli, R. Spagna and D. Viterbo, J. Appl. Crystallogr., 1989, 22, 389 CrossRef CAS.
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