View PDF Version
 
DOI: 10.1039/A906244K (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1999, 2701-2706

Synthesis and crystal structure of the bromide salt of the inside protonated form of the cage amine [(2.3)3]adamanzane, 1,4,8,12-tetraazatricyclo[6.6.3.24,12]nonadecane and synthesis of the bowl amine [(2.3)2.21]adamanzane, 1,5,9,12-tetraazabicyclo[7.5.2]hexadecane

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

Johan Springborg, Bente Nielsen, Carl Erik Olsen and Inger Søtofte

Abstract

The reaction of 1,4,7-triazacyclononane with tris(3-chloropropyl)amine affords the inside monoprotonated form of the tricyclic amine 1,4,8,12-tetraazatricyclo[6.6.3.24,12]nonadecane (3), which was isolated as the bromide salt, [H[(2.3)3]adz]Br (yield 38%). The crystal structure of [H[(2.3)3]adz]Br·4H2O has been solved by X-ray diffraction at T = 120 K. In the i+,i,i,i-H[(2.3)3]adz+ cation (3a) the acidic hydrogen atom and the lone pairs of the nitrogen atoms are oriented towards the inside of the cavity. The acidic hydrogen atom is attached to the apical nitrogen atom and both are positioned on a three-fold axis. The distances between the nitrogen atoms are in the range of 2.73(2)–2.99(1) Å. The inside coordinated proton in H[(2.3)3]adz+ (3a) is unusually inert to reaction with base (kdiss < 4 × 10–9 s–1 at 25 °C in 0.01 M NaOD). From 1H and 13C NMR it is concluded that in slightly acidic (pH > 2) and in basic aqueous solutions the dominant form of the cage has all four lone pairs pointing into the cavity. In concentrated strong acid protonation occurs and is believed to involve inversion at one or several of the bridgehead nitrogen atoms. In concentrated boiling hydrochloric acid the cage undergoes a slow cleavage of one trimethylene bridge to give the bowl amine [(2.3)2.21]adz (7), 1,5,9,12-tetraazabicyclo[7.5.2]hexadecane, which was isolated as the triprotonated bromide dichloride salt, [H3[(2.3)2.21]adz]BrCl2·H2O (yield 40%).

References

  1. A. M. Sargeson, Pure Appl. Chem., 1984, 56, 1603 CAS.
  2. E. Kimura, Top. Curr. Chem., 1985, 128, 113 CAS.
  3. A. Bianchi, M. Micheloni and P. Paoletti, Pure Appl. Chem., 1988, 60, 525 CrossRef CAS.
  4. M. Micheloni, Comments Inorg. Chem., 1988, 8, 79 CAS.
  5. R. W. Alder, Chem. Rev., 1989, 89, 1215 CrossRef CAS.
  6. R. D. Hancock and A. E. Martell, Chem. Rev., 1989, 89, 1875 CrossRef CAS.
  7. R. W. Alders, Tetrahedron, 1990, 46, 683 CrossRef CAS.
  8. B. Dietrich, P. Viout and J.-M. Lehn, Macrocyclic Chemistry, VCH, Weinheim, Germany, 1993 Search PubMed.
  9. Comprehensive Supramolecular Chemistry, Vol. 1, ed. G. W. Gokel, Elsevier Science Ltd, Oxford, 1996 Search PubMed.
  10. F. P. Schmidtchen, Pure Appl. Chem., 1989, 61, 1535 CrossRef CAS and references cited therein.
  11. H. Takemura, T. Hirakawa, T. Shinmyozu and T. Inazu, Tetrahedron Lett., 1984, 25, 5053 CrossRef CAS.
  12. E. Graf, J. P. Kintzinger, J.-M. Lehn and J. LeMoigne, J. Am. Chem. Soc., 1982, 104, 1672 CrossRef CAS and references cited therein.
  13. J. Springborg, C. E. Olsen and I. Søtofte, Acta Chem. Scand., 1995, 49, 555 CAS.
  14. J. Springborg, U. Pretzmann and C. E. Olsen, Acta Chem. Scand., 1996, 50, 294 CrossRef CAS.
  15. J. Springborg, U. Pretzmann, C. E. Olsen and I. Søtofte, Acta Chem. Scand., 1998, 52, 289 CrossRef CAS.
  16. Y. Miyahara, Y. Tanaka, K. Amimoto, T. Akazawa, T. Saguragi, H. Kobayashi, K. Kubota, M. Suenaga, H. Koyama and T. Inazu, Angew. Chem., Int. Ed., 1999, 38, 956 CrossRef CAS.
  17. K. N. Robertson, P. K. Bashi, S. D. Lantos, T. S. Cameron and O. Knop, Can. J. Chem., 1998, 76, 583 CrossRef CAS.
  18. S. T. Howard and I. A. Fallis, J. Org. Chem., 1998, 63, 7117 CrossRef CAS.
  19. J. Springborg, P. Kofod, C. E. Olsen, H. Toftlund and I. Søtofte, Acta Chem. Scand., 1995, 49, 547 CrossRef CAS.
  20. J. Springborg, U. Pretzmann, B. Nielsen, C. E. Olsen and I. Søtofte, Acta Chem. Scand., 1998, 52, 212 CrossRef CAS.
  21. J. Springborg and I. Søtofte, Acta Chem. Scand., 1997, 51, 357 CrossRef CAS.
  22. J. Springborg, J. Glerup and I. Søtofte, Acta Chem. Scand., 1997, 51, 832 CrossRef CAS.
  23. R. Sanzenbacher, I. Søtofte and J. Springborg, Acta Chem. Scand., 1999, 53, 457 CrossRef CAS.
  24. G. R. Weisman, M. E. Rogers, E. H. Wong, J. P. Jasinski and E. S. Paight, J. Am. Chem. Soc., 1990, 112, 8604 CrossRef CAS.
  25. G. R. Weisman, E. H. Wong, D. C. Hill, M. E. Rogers, D. P. Reed and J. C. Calabrese, Chem. Commun., 1996, 947 RSC.
  26. T. J. Hubin, J. M. McCormick, S. R. Collin, N. W. Alcock and D. H. Busch, Chem. Commun., 1998, 1675 RSC.
  27. W. Niu, E. H. Wong, G. R. Weisman, K.-C. Lam and A. L. Rheingold, Inorg. Chem. Commun., 1999, 2, 361 CrossRef CAS.
  28. G. H. Searle and R. J. Geue, Austr. J. Chem., 1984, 37, 959 CAS.
  29. T. H. Cooper, M. J. Mayer, K.-H. Leung, L. A. Ochrymowycz and D. B. Rorabacher, Inorg. Chem., 1992, 31, 3796 CrossRef CAS; F. E. Hahn and S. Rupprecht, Chem. Ber., 1991, 124, 481 CAS.
  30. H. D. Flack and D. Schwarsenbach, Acta Crystallogr., Sect. A, 1988, 44, 499 CrossRef.
  31. H. D. Flack, Acta Crystallogr., Sect. A, 1983, 39, 876 CrossRef.
  32. Siemens, SMART and SAINT, Area-Detector Control and Integration Software, Bruker AXS Analytical X-ray Systems, Madison, Wisconsin, USA, 1995.
  33. G. M. Sheldrick, SADABS, Program for Absortion Correction, Bruker AXS Analytical X-ray Systems, Madison, Wisconsin, USA, 1996.
  34. G. M. Sheldrick, SHELXTL95, Bruker AXS Analytical X-ray Systems, Madison Wisconsin, USA, 1995.
  35. A. L. Spek, Acta Crystallogr., Sect. A, 1990, 46, C-34.
Click here to see how this site uses Cookies. View our privacy policy here.