One-pot Synthesis of a 1,3,7,9-Tetraazacyclododecane Derivative and an Investigation of its Complexation Properties

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

Andreas Axén, Helena Grennberg and Adolf Gogoll


Abstract

A one-pot synthesis of a 1,3,7,9-tetraazacyclododecane macrocycle in 37% yield from inexpensive starting materials is described, and its complexation properties with metal cations are investigated.


References

  1. K. Bowman-James, in Encyclopedia of Inorganic Chemistry, ed. R. B. King, Wiley, Chichester, 1994, vol. 4, pp. 1999–2016 Search PubMed.
  2. D. Landini, A. Maia, F. Montanari and P. Tundo, J. Am. Chem. Soc., 1979, 101, 2526 CrossRef CAS.
  3. V. Alexander, Chem. Rev., 1995, 95, 273 CrossRef CAS.
  4. R. B. Lauffer, Chem. Rev., 1987, 87, 901 CrossRef CAS.
  5. E. Kimura, Pure Appl. Chem., 1993, 65, 355 CrossRef CAS; R. Hettich and H.-J. Schneider, J. Am. Chem. Soc., 1997, 119, 5638 CrossRef.
  6. J.-P. Behr and J.-M. Lehn, in Design of Synthetic Molecular Receptors and Catalysts in Structural and Functional Aspects of Enzyme Catalysis, ed. H. Eggerer and R. Huber, Springer, Berlin, Heidelberg, New York, 1981 Search PubMed.
  7. Reviews: H.-Y. An, J. S. Bradshaw and R. M. Izatt, Chem. Rev., 1992, 92, 543 Search PubMed; K. E. Krakowiak, J. S. Bradshaw and R. M. Izatt, Synlett, 1993, 611 CrossRef CAS.
  8. A. V. Bordunov, J. S. Bradshaw, V. N. Pastushok and R. M. Izatt, Synlett, 1996, 933 CrossRef.
  9. M. C. Thompson and D. H. Busch, J. Am. Chem. Soc., 1964, 86, 3651 CrossRef CAS.
  10. H. Krässig, Makromol. Chem., 195/196, 17, 77 Search PubMed.
  11. M. K. Moi and C. F. Meares, J. Am. Chem. Soc., 1988, 110, 6266 CrossRef CAS; M. L. Garrity, G. M. Brown, J. E. Elbert and R. A. Sachleben, Tetrahedron Lett., 1993, 34, 5531 CrossRef CAS.
  12. A. Gogoll, H. Grennberg and A. Axén, Organometallics, 1997, 16, 1167 CrossRef CAS.
  13. Synthesis: N-methylenebenzylamine (0.60 g, 5 mmol), dimethyl malonate (0.33 g, 2.5 mmol) and paraformaldehyde (30% aq. solution)(0.5 g, 5 mmol) were mixed in ethanol (30 mL) then refluxed with stirring for 20 h. The solvent was removed and the product 1 purified by column chromatography (Silica 60; pentane–diethyl ether, 7:3); yield 0.7 g, 37%, clear oil. 1H NMR (400 MHz, CDCl3)δ 7.40–7.20 (m, 20 H), 3.71 (s, 12 H), 3.61 (s, 8 H), 3.22 (br s, 4 H), 3.02 (br s, 8 H); 13C NMR (100.6 MHz, CDCl3)δ 169.4, 137.5, 128.7, 123.0, 126.9, 74.3, 59.0, 55.5, 54.0, 52.4; IR (CDCl3) 3061, 2819, 1736, 1495, 1453, 1263 cm–1; calc. for C44H52N4O8 C 69.09, H 6.85, N 7.32; found C 69.00, H. 6.87, N 7.22%; MS (electrospray, methanol solution), m/z= 765 ([M+ H]+).
  14. Synthesis: Benzylamine (10.9 mL, 0.1 mol) and formaldehyde (0.1 mol, 8.6 mL 35% aq. solution) were mixed in ethanol (50 mL) and refluxed overnight. The solvent was removed yielding compound 2 as a clear oil that crystallised over time (10.1 g, 85%), mp 49–50 °C. 1H NMR (400 MHz, CDCl3)δ 7.40–7.20 (m, 5 H), 3.70 (s, 2 H), 3.45 (s br, 2 H); 13C NMR (100.6 MHz, CDCl3)δ 138.3, 128.8, 128.1, 126.9, 73.7, 57.0; IR (CDCl3) 3050, 2900, 1490, 1450 cm–1.
  15. At lower temperatures (–60 °C) the methylene proton signals (two br s) separate into two pairs of doublets. Compare, e.g. I. Lazar, D. C. Hrncir, W. D. Kim, G. E. Kiefer and A. D. Sherry, Inorg. Chem., 1992, 31, 4422 Search PubMed.
  16. E. Mei, L. Liu, J. L. Dye and A. I. Popov, J. Solution Chem., 1977, 6, 771 CAS; Y. Jayathirtha and V. Krishnan, Indian J. Chem., Sect-A, 1979, 18, 311 Search PubMed.
  17. 23Na NMR (ambient temperature, 39.35 MHz); sodium perchlorate (0.05 M, solvent THF or acetone), addition of ligand 1(0.50M in the respective solvent). Acetone solution: no chemical shift change of 23Na, indicating absence of complexation. THF solution: small, continuous increase of 23Na chemical shift, indicating a weak complexation.18.
  18. J. D. Lin and A. I. Popov, J. Am. Chem. Soc., 1981, 103, 3773 CrossRef CAS.
  19. R. M. Izatt, J. S. Bradshaw, S. A. Nielsen, J. D. Lamb and J. J. Christensen, Chem. Rev., 1985, 85, 271 CrossRef CAS.
  20. M. Kodama, E. Kimura and S. Yamaguchi, J. Chem. Soc., Dalton Trans., 1980, 2536 RSC.
  21. J. F. Desreux, E. Merciny and M. F. Loncin, Inorg. Chem., 1981, 20, 987 CrossRef CAS.
  22. J.-M. Lehn and F. Montavon, Helv. Chim. Acta, 1978, 61, 67 CrossRef CAS.
  23. R. D. Hancock, Acc. Chem. Res., 1990, 23, 253 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.