View PDF Version
 
DOI: 10.1039/A901632E (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1999, 1087-1094

(2-Pyridyl)iminopropadienone

(Note: The full text of this document is currently only available in the PDF Version )

Carsten Plüg, Wilhelm Frank and Curt Wentrup

Abstract

(2-Pyridyl)iminopropadienone 13 is generated by flash vacuum thermolysis (FVT) of 2-substituted pyrido[1,2-a]pyrimidin-4-ones 9 and observed by IR spectroscopy. Addition of HCl to 13 causes reversion to the starting material 9b, whereas addition of nucleophiles leads to malonic acid imide derivatives (23, 24, 26, 27, 28). The latter undergo thermal elimination of amines to regenerate 2-substituted pyridopyrimidinones. A competing retro-ene reaction occurs on FVT of 2-(dialkylamino)pyridopyrimidinones 9c,d, presumably in the oxoketenimine intermediates 22/25, with formation of the unsubstituted pyridopyrimidinone 31.

References

  1. (a) T. Mosandl, C. O. Kappe, R. Flammang and C. Wentrup, J. Chem. Soc., Chem. Commun., 1992, 1571 RSC; (b) T. Mosandl, S. Stadtmüller, M. W. Wong and C. Wentrup, J. Chem. Phys., 1994, 98, 1080 CAS.
  2. C. Wentrup, B. E. Fulloon, D. W. J. Moloney, H. Bibas and M. W. Wong, Pure Appl. Chem., 1996, 68, 891 CAS.
  3. D. W. J. Moloney, M. W. Wong, R. Flammang and C. Wentrup, J. Org. Chem., 1997, 62, 4240 CrossRef CAS.
  4. B. E. Fulloon and C. Wentrup, J. Org. Chem., 1996, 61, 1363 CrossRef CAS; B. E. Fulloon, H. A. A. El-Nabi, G. Kollenz and C. Wentrup, Tetrahedron Lett., 1995, 36, 6547 CrossRef CAS.
  5. C. Wentrup, W. Frank, B. E. Fulloon, D. W. J. Moloney, T. Mosandl and V. V. R. Rao, J. Org. Chem., 1999, 64 Search PubMed in the press.
  6. F.-C. Ye, B.-C. Chen and X. Huang, Synthesis, 1989, 317 CrossRef CAS.
  7. A. E. Tschitschibabin, Ber. Dtsch. Chem. Ges., 1924, 57, 1168.
  8. (a) A. R. Katritzky and A. J. Waring, J. Chem. Soc., 1962, 1544 RSC; (b) P. Dvortsak, G. Resofszki, L. Zalantai and A. I. Kiss, Tetrahedron, 1976, 32, 2117 CrossRef CAS; (c) N. Thorup and O. Simonsen, Acta Crystallogr., Sect. C, 1985, 41, 472 CrossRef.
  9. C. Plüg, G. Clark and C. Wentrup, unpublished work.
  10. H. R. Snyder and M. M. Robison, J. Am. Chem. Soc., 1952, 74, 4910 CrossRef CAS.
  11. V. Oakes and H. N. Rydon, J. Chem. Soc., 1958, 209 RSC.
  12. V. V. Ramana Rao and C. Wentrup, J. Chem. Soc., Perkin Trans. 1, 1988, 2583 Search PubMed.
  13. C. Plüg and C. Wentrup, Acta Chem. Scand., 1998, 51, 654.
  14. C. Plüg, B. Wallfisch and C. Wentrup, unpublished work.
  15. Protonation of RNC3O: R. Flammang, Y. V. Haverbeke, M. W. Wong, A. Rühmann and C. Wentrup, J. Phys. Chem., 1994, 98, 4814 Search PubMed Protonation of C3O2: J. Tortajada, G. Provot, J. P. Morizur, J.-F. Gal, P.-C. Maria, R. Flammang and Y. Govaert, Int. J. Mass Spectrom. Ion. Proc., 1995, 141, 241 CrossRef CAS Cf. also N. Pietri, T. Chiavassa, A. Allouche and J.-P. Aycard, J. Phys. Chem. A, 1997, 101, 1093 Search PubMed.
  16. Free energies of activation calculations according to e.g.F. A. Bovey, Nuclear Magnetic Resonance Spectroscopy, Academic Press, San Diego, 1988. The estimated error is less than 1 kcal mol–1 Search PubMed.
  17. H. Bibas, R. Koch and C. Wentrup, J. Org. Chem., 1998, 63, 2619 CrossRef CAS.
  18. C. O. Kappe, M. W. Wong and C. Wentrup, J. Org. Chem., 1995, 60, 1686 CrossRef CAS.
  19. H. Briehl, A. Lukosch and C. Wentrup, J. Org. Chem., 1984, 49, 2772 CrossRef CAS.
  20. C. Wentrup, R. Blanch, H. Briehl and G. Gross, J. Am. Chem. Soc., 1988, 110, 1874 CrossRef CAS.
  21. G. Kobayashi, Y. Matsuda, R. Natsuka, Y. Tominaga and C. Maseda, Yakugaku Zasshi, 1974, 94, 44 CAS; Chem. Abstr., 1974, 80, 108477b Search PubMed.
  22. G. Roma, A. Ermili, M. Di Braccio and M. Mazzei, Farmaco Ed. Sci., 1982, 37, 747 Search PubMed; Chem. Abstr., 1983, 98, 53825c Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.