A di-aza-benzo crown ether derived fromp-tert-butyl calix[4]arene. Synthesis and complexation of zinc cation

  • Ratana Seangprasertkij
  • Zouhair Asfari
  • Jacques Vicens
Research Communication


Di-aza-benzo crown etherp-tert-butyl calix[4]arene (1) has been prepared by hydrogenating the already known Schiff-base precursor (2). The metal ion complexing ability of (1) toward zinc cation is presented. The formation of a 2:1 (Zn: (1) complex and the location of zinc cations were deduced from1H-NMR investigations.

Key words

1,3-Bridgedp-tert-butyl calix[4]arene complexation of zinc cation 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    C.D. Gutsche inCalixarenes, Monographs in Supramolecular Chemistry, J.F. Stoddart (ed.), The Royal Society of Chemistry, Cambridge (1989).Google Scholar
  2. 2.
    J. Vicens and V. Böhmer inCalixarenes: A Versatile Class of Macrocyclic Compounds, Kluwer Academic Publishers, Dordrecht (1991).Google Scholar
  3. 3.(a)
    C. Alferi, E. Dradi, A. Pochini, R. Ungaro and G.D. Andreetti:J. Chem. Soc., Chem. Commun., 1075 (1983).Google Scholar
  4. 3(b).
    R. Ungaro, A. Pochini and G.D. Andreetti:J. Incl. Phenom. 2, 199 (1984).Google Scholar
  5. 4.
    P.J. Dijkstra, J.A. Brunink, K.-E. Bugge, D.N. Reinhoudt, S. Harkema, R. Ungaro, F. Ugozzoli and E. Ghidini:J. Am. Chem. Soc. 111, 7576 (1989) and references therein.Google Scholar
  6. 5.
    P.D. Beer, J.P. Martin and M.G.B. Drew:Tetrahedron 48, 9917 (1992).Google Scholar
  7. 6.
    R. Ostazewski, T.M. Stevens, W. Verboom and D.N. Reinhoudt:Recl. Trav. Chim. Pays-Bas 110, 294 (1991).Google Scholar
  8. 7.
    V. Böhmer, G. Ferguson, J.F. Gallagher, A.L. Lough, M.A. McKervey, E. Madigan, M.B. Moran, J. Phillips and G. Williams:J. Chem. Soc. Perkin Trans. 1, 1521 (1993).Google Scholar
  9. 8.
    R. Seangprasertkij, Z. Asfari, F. Arnaud, J. Weiss and J. Vicens:J. Incl. Phenom. 14, 141 (1992).Google Scholar
  10. 9.(a)
    C.W.G. Ansell, K.P. Dancy, M. McPartlin and P.A. Tasker:J. Chem. Soc. Dalton Trans., 1789 (1983).Google Scholar
  11. 9(b).
    L.F. Lindoy, H.C. Lip, J.H. Rea, R.J. Smith, K. Henrick, M. McPartlin and P.A. Tasker:Inorg. Chem. 19, 3360 (1980).Google Scholar
  12. 9(c).
    S.J. Kim, J.H. Kim, H. Huh and K.S. Choi:Pure Appl. Chem. 65, 499 (1993).Google Scholar
  13. 10.
    A typical procedure is described for the preparation of (1): Schiff-base calix[4]arene (2) (10.00 g, 10.2 mmol) was stirred with sodium borohydride (7.84 g, 203.6 mmol) in tetrahydrofuran under a nitrogen atmosphere for two hours. After completion of the reaction, the unreacted sodium borohydride was quenched with water. After evaporating to dryness, the solid residue was then extracted with dichloromethane. The organic layer was dried over sodium sulfate and evaporated to dryness. The solid was acidified with a hydrochloric acid solution in methanol (0.74% v/v) until the pH of the solution reached 1. The hydrogenated product was obtained as a white solid in protonated form, (1).2HCl. Yield: 9.86 g, 91%. Mp 277.1–277.6°C (dec). The di-aza-benzo crown ether-p-tert-butylcalix[4]arene (1) was obtained by neutralizing (1). 2HCl (2.00 g, 1.9 mmol) with NaOH (0.20 g, 5.0 mmol) in methanol (75 mL). A white precipitate was observed upon contact of the reactants. The solvent was evaporated to dryness under reduced pressure and the residue was extracted into dichloromethane. After drying over sodium sulfate, (1) was precipitated from the dichloromethane solution by adding methanol. Yield: 1.46 g, 79%. Mp 280.7–281.1°C (dec.).Characterization data for (1).2HCl1H-NMR (CDCl3): 9.66 (s, broad, 4H, NH), 7.40–7.30 and 6.95–6.90 (m, 8H, aromatic protons), 6.99 (s, 4H, HOArH), 6.82 (s, 2H, ArOH), 6.74 (s, 4H, ROArH), 4.68 (b, 4H, Ar−CH 2−NH−), 4.39 and 3.24 (AB system, JH-H=13.0 Hz, 8H, ArCH A H BAr), 4.23 (s, broad, 8H, OCH 2CH 2O), 3.70 (s, broad, 4H, NCH 2CH2), 2.90 (s, broad, 2H, CH2CH 2CH2), 1.25 (s, 18H, HOAr-t-C4H9), 0.88 (s, 18H, ROAr-t−C4 H 9). FAB positive: 987.4. Anal. Calcd. for C65H82O6N2.2HCl.3CH3OH(1156.42): C, 70.63; H, 8.37. Found: C, 70.78; H, 8.38. For (1)1H-NMR (CDCl3): 7.25–7.18 and 6.95–6.79 (m, 8H, aromatic protons), 7.04 (s, 4H, HOArH), 6.67 (s, 4H, ROArH), 6.36 (s, 2H, NH), 4.40 and 4.22 (broad, 8H, OCH 2O), 4.38 and 3.26 (AB system, JH-H=13.2 Hz, 8H, ArCH a H BAr), 3.86 (s, 4H, Ar−CH 2−NH-), 2.53 (t, JH-H=5.4 Hz, 4H,NCH 2CH2), 1.48 (m, 2H, CH2CH 2CH2), 1.30 (s, 18H, HOAr-t-C4 H g), 0.87 (s, 18H, ROAr-t-C4 H 9). FAB positive: 987.4. Anal. Calcd. for C65H82O6N2 (986.62): C, 79.07; H, 8.37. Found: C,79.79; H, 8.42.Google Scholar
  14. 11.
    The solutions for NMR complexation study were prepared by adding the methanol solution of Zn(CLO4)2. 6H2O into the chloroform solution of (1) so that the Zn2+: (1) mole ratio varied from 0 to 6. The concentration of (1) remained constant at 2.0×10−2M. The spectra were followed until no more shifts were observed after 26 days.Google Scholar
  15. 12.
    E. Mei, J.L. Dye and A.I. Popov:J.Am. Chem. Soc. 99, 5302 (1977)Google Scholar
  16. 13.
    E. Mei, A.I. Popov and J.L. Dye:J. Am. Chem. Soc. 99, 6523 (1977).Google Scholar
  17. 14.
    This procedure was adopted from [15]: (1) (0.17g, 0.2 mmol) in chloroform was mixed with NaOH (16 mg, 0.4 mmol) and Zn(ClO4)2. 6H2O (0.29 g, 1.1 mmol) in methanol and the reaction mixture was stirted for two days. After evaporation to dryness, chloroform was added and the unreacted zinc salt was filtered off. The filtrate gave (3) upon standing for two days as yellowishwhite needles.Characterization data for (3)1H-NMR (CDCl3): 7.43–7.34 and 7.02–6.94 (m, 8H, aromatic protons), 7.05 (s, 4H, HOArH),6.63 (s, 4H, ROSrH), 6.18 (s, 2H, NH), 4.58 and 4.37 (broad, 8H, OCH 2CH 2O), 4.46 (s, 4H, Ar−CH 2−N), 4.23 and 3.29 (AB system, JH-H=13.4 Hz, 8H, ArCH A H BAr), 3.52 (broad, 4H, NCH 2CH2), 2.70 (m, 2H, CH2CH 2CH2), 1.29 (s, 18H, HOAr-t-C4 H 9), 0.83 (s, 18H, ROAr-t-C4 H 9).Google Scholar
  18. 15(a).
    E. Kimura, T. Koike and K. Toriumi:Inorg. Chem. 27, 3687 (1988).Google Scholar
  19. 15.(b)
    E. Kimura, T. Shiota, T. Koike, M. Shiro and M. Kodama:J. Am. Chem Soc. 112, 5805 (1990).Google Scholar
  20. 15.(c)
    T. Koira, E. Kimura, I. Nakamura and M. Shiro:J. Am. Chem. Soc. 114, 7338 (1992).Google Scholar
  21. 15.(d)
    E. Kimura, M. Sjionaya, A. Hoshino, T. Ikeda and Y. Yamada:J. Am. Chem. Soc. 114, 10134 (1992).Google Scholar

Copyright information

© Kluwer Academic Publishers 1994

Authors and Affiliations

  • Ratana Seangprasertkij
    • 1
  • Zouhair Asfari
    • 2
  • Jacques Vicens
    • 2
  1. 1.Department of ChemistryChulalongkorn UniversityBangkokThailand
  2. 2.E.H.I.C.S.URA 405 du C.N.R.S.StrasbourgFrance

Personalised recommendations