1,3-Diaza-2-azoniaallene salts: cycloadditions to alkynes, carbodiimides and cyanamides

Abstract

1,3-Diaza-2-azoniaallene salts 2 react with alkynes 6 to furnish 1,2,3-triazolium salts 7a–m. According to AM1 calculations, these reactions are concerted [3 + 2] cycloadditions (1,3-dipolar cycloadditions with inverse electron demand). The structure of the triazolium salt 7e has been confirmed by X-ray crystallographic analysis. With N,N′-dialkylcarbodiimides 9 the heteroallene salts 2 undergo cycloaddition to furnish 1,3,4,5-tetra-substituted 4,5-dihydrotetrazolium salts 11, which on heating in acetonitrile eliminate an alkene to afford 1,3,5-tri-substituted tetrazolium salts 12. Furthermore, it has been found that heteroallene salts 2 react with N,N-dialkylcyanamides 13 to give 1,3,5-tri-substituted tetrazolium salts 15. Here, AM1 calculations suggest stepwise cycloaddition mechanisms via intermediate nitrilium salts 10 and 14 respectively.

References

1. A. Schmidt, Chem. Ber., 1966, 99, 2976.
2. W. Pritzkow and G. Pohl, J. Prakt. Chem., 1963, 292, 132.
3. J. Goubeau, E. Allenstein and A. Schmidt, Chem. Ber., 1964, 97, 884.
4. N. Wiberg and K. H. Schmid, Angew. Chem., 1964, 76, 381; Angew. Chem., Int. Ed. Engl., 1964, 3, 444.
5. A. Mertens, K. Lammertsma, M. Arvanaghi and G. A. Olah, J. Am. Chem. Soc., 1983, 105, 5657.
6. R. Glaser and G. S. Choy, J. Phys. Chem., 1991, 95, 7682.
7. K. O. Christie, W. W. Wilson, D. A. Dixon, S. I. Khan, R. Bau, T. Metzenthin and R. Lu, J. Am. Chem. Soc., 1993, 115, 1836.
8. W. Wirschun and J. C. Jochims, Synthesis, 1997, 233.
9. W. Wirschun, G.-M. Maier and J. C. Jochims, Tetrahedron, 1997, 53, 5755.
10. N. Al-Masoudi, N. A. Hassan, Y. A. Al-Soud, P. Schmidt, A. E. M. Gaafar, M. Weng, S. Marino, A. Schoch, A. Amer and J. C. Jochims, J. Chem. Soc., Perkin Trans. 1, 1998, 947.
11. Q. Wang, J. C. Jochims, S. Köhlbrandt, L. Dahlenburg, M. Al-Talib, A. Hamed and A. E. Ismail, Synthesis, 1992, 710.
12. Q. Wang, A. Amer, S. Mohr, E. Ertel and J. C. Jochims, Tetrahedron, 1993, 49, 9973.
13. R. Sustmann, Pure Appl. Chem., 1974, 40, 569.
14. D. I. Rawson, B. K. Carpenter and H. M. R. Hoffmann, J. Am. Chem. Soc., 1979, 101, 1786.
15. H. M. R. Hoffmann and U. Karama, Chem. Ber., 1992, 125, 2803.
16. H. Takaya, S. Makino, Y. Hayakawa and R. Noyori, J. Am. Chem. Soc., 1978, 100, 1765.
17. S. Parsons, J. Passmore, M. J. Schriver and X. Sun, Inorg. Chem., 1991, 30, 3342.
18. N. Burford, J. P. Johnson, J. Passmore, M. J. Schriver and P. S. White, J. Chem. Soc., Chem. Commun., 1986, 966.
19. S. W. Liblong, R. T. Oakley, A. W. Cordes and M. C. Noble, Can. J. Chem., 1983, 61, 2062.
20. Q. Wang, A. Amer, C. Troll, H. Fischer and J. C. Jochims, Chem. Ber., 1993, 126, 2519.
21. Q. Wang, M. Al-Talib and J. C. Jochims, Chem. Ber., 1994, 127, 541.
22. Q. Wang, S. Mohr and J. C. Jochims, Chem. Ber., 1994, 127, 947.
23. Y. Guo, Q. Wang and J. C. Jochims, Synthesis, 1996, 274.
24. Y. A. Al-Soud, W. Wirschun, N. A. Hassan, G.-M. Maier and J. C. Jochims, Synthesis, in the press.
25. MOPAC program, ver 6.0, J. J. P. Stewart, QCPE # 455; all calculations were carried out with complete optimization of all bond angles and dihedral angles.
26. Full crystallographic details, excluding structure factor tables, have been deposited at the Cambridge Crystallographic Data Centre (CCDC). For details of the deposition scheme, see ‘Instructions for Authors’, J. Chem. Soc., Perkin Trans. 1, available via the RSC Web page (http://www.rsc.org/authors). Any request to the CCDC for this material should quote the full literature citation and the reference number 207/219.
27. G. Boche, P. Andrews, K. Harms, M. Marsch, K. S. Rangappa, M. Schimeczek and C. Willeke, J. Am. Chem. Soc., 1996, 118, 4925.
28. K. T. Finley, 1,2,3-Triazolium, Triazolinium and Meso-Ionic Compounds, in The Chemistry of Heterocyclic Compounds, series ed. A. Weissberger and E. C. Taylor, Wiley, New York, 1980, vol. 39, p. 292(ed. J. A. Montgomery).
29. T. Isida, S. Kozima, S. Fujimori and K. Sisido, Bull. Chem. Soc. Jpn., 1972, 45, 1471.
30. H. Quast, A. Fuβ and U. Nahr, Chem. Ber., 1985, 118, 2164.
31. D. Moderhack and A. Lembcke, J. Chem. Soc., Perkin Trans. 1, 1986, 1157.
32. I. Y. Shirobokov, M. V. Chekushina, V. A. Ostrovskii, G. I. Koldobskii and G. B. Erusalimskii, Khim. Geterotsikl. Soedin., 1988, 24, 502.
33. G. M. Sheldrick, SHELX-86 and SHELX-93, University of Göttingen, 1986, resp. 1993.
34. C. D. Hurd and A. Tockman, J. Org. Chem., 1958, 23, 1087.
35. J. Mintz and C. Walling, Org. Synth., 1973, Coll. vol. V, 184.
36. G. Vernin, C. Siv and J. Metzger, Synthesis, 1977, 691.
37. K. Bott, Angew. Chem., 1965, 77, 132; Angew. Chem., Int. Ed. Engl., 1965, 4, 148.