Skip to main content
SpringerLink
Log in

Hard–Soft Receptors, Tetrakis[(N,N-diethylaminocarbonyl)methoxy] thiacalix[4]arene Derivatives with cone and 1,3-alternate Conformation

  • Published:
Journal of inclusion phenomena and macrocyclic chemistry Aims and scope Submit manuscript

Abstract

Direct O-alkylation of p-tert-butyltetrathiacalix[4]arene with N,N-diethylchloroacetamide afforded two conformational isomers (1,3-alternate and cone) of tetrakis[(N,N-diethylaminocarbonyl)methoxy]thiacalix[4]arene and 1,3-disubstituted bis[(N,N-diethylaminocarbonyl)methoxy]thiacalix[4]arene, depending on the base used. The complaxation behaviors of the tetrakis isomers were assessed by 1H NMR titration experiments. Evidence of 1:2 (homo- and hetero-dinuclear) complexes formation of 1,3-alternate-tetrakis[(N,N-diethylaminocarbonyl)methoxy]thiacalix[4]arene with alkali (K+ and Na+) or transition (Ag+) metal ions was obtained. Interestingly, it was found that the cone-tetrakis[(N,N-diethylaminocarbonyl)methoxy]thiacalix[4]arene required a prior Ag+ complexation to form 1:2 heterodinuclear complex.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. (a) H. Kumagi, M. Hasegawa, S. Miyanari, Y. Sugawa, Y. Sato, T. Hori, S. Ueada, H. Kamiyama, and S. Miyano: Tetrahedron Lett. 38, 3971 (1997). For a comprehensive review of all aspects of calixarene chemistry, see: (b) C.D. Gutsche: Calixarenes, The Royal Society of Chemistry, Cambridge (1989); (c) C.D. Gutsche: Acc. Chem. Res. 16, 161 (1983). (d) J. Vicens and V. Böhmer: Calixarenes: A Versatile Class of Macrocyclic Compounds, Kluwer Academic Publishers, Cambridge (1990); (e) S. Shinkai: In G.W. Gokel (ed.), Advances in Supramolecular Chemistry, Vol. 3, Jai press inc ltd., London (1993), 97 pp: (f) V. Böhmer: Angew. Chem. Int. Ed. Engl. 34, 713 (1995); (g) C.D. Gutsche: Calixarenes Revisited, Royal Society of Chemistry, Cambridge (1998).

  2. (a) K. Iwamoto and S. Shinkai: J. Org. Chem. 57, 7066 (1992). (b) N. Iki, F. Marumi, T. Fujimoto, N. Morohashi, S. Miyano: J. Chem. Soc. Perkin Trans.2, 2745 (1998).

  3. P. Lhoták M. Himl I. Stibor H. Petrícková (2002) Tetrahedron Lett. 43 9621 Occurrence Handle10.1016/S0040-4039(02)02391-2

    Article  Google Scholar 

  4. T. Yamato F. Zhang K. Kumamaru H. Yamamoto (2002) J. Incl. Phenom. 42 51 Occurrence Handle10.1023/A:1014540609454

    Article  Google Scholar 

  5. (a) A. Arduini, E. Ghidini, A. Pochini, R. Ungaro, G.D. Andreetti, G. Calestani, and F. Ugozzoli: J. Incl. Phenom. 6, 119 (1988); (b) H. Matsumoto, S. Nishino, M. Takeshita, S. Shinkai: Tetrahedron 51, 4647 (1995); (c) N.J. Wolf, E.M. Georgiev, A.T. Yordanov, B.R. Whittlesey, H.F. Kock, D. M. Roundhil: Polyhedron 18, 885 (1999).

  6. (a) N. Sabbatinim, M. Guardigli, A. Mecati, V. Balzani, R. Ungaro, E. Ghidini, A. Casnati, and A. Pochini: J. Chem. Soc., Chem. Commun. 878 (1990); (b) H. Kumagai, M. Hasegawa, S. Miyanari, Y. Sugawa, Y. Sato, T. Hori, S. Ueda, H. Kamiyama, and S. Miyano: Tetrahedron Lett. 38, 3971 (1997).

  7. R. Lamartine C. Bavoux F. Vocason A. Martin G. Senlis M. Perrin (2001) Tetrahedron Lett. 42 1021 Occurrence Handle10.1016/S0040-4039(00)02131-6

    Article  Google Scholar 

  8. H.A. Benesi J.H. Hildebrand (1949) J. Am. Chem. Soc. 71 2073 Occurrence Handle10.1021/ja01176a030

    Article  Google Scholar 

  9. (a) P. Lhoták, L. Kaplanek, I. Stibor, J. Lang, H. Dvorákova, R. Hrabal, and J. Sykora: Tetrahedron Lett. 41, 9339 (2000). (b) N. Iki, N. Morohashi, F. Narumi, T. Fujimoto, T. Suzuki, and S. Miyano: Tetrahedron Lett.40, 7337 (1999).

  10. T. Yamato T. Iwasa F. Zhang (2001) J. Incl. Phenom 39 285 Occurrence Handle10.1023/A:1011144209597

    Article  Google Scholar 

  11. (a) N. Iki, N. Morohashi, F. Narumi, and S. Miyano: Bull. Chem. Soc. Jpn. 71, 1597 (1998); (b) N. Iki, H. Kumagai, N. Morohashi, K. Ejima, M. Hasegawa, S. Miyanari, and S. Miyano: Tetrahedron Lett. 39, 7559 (1998); (c) N. Morohashi, T. Hattori, K. Yokomakura, C. Kabuto, F. Narumi, T. Fujimoto, T. Suzuki, and S. Miyano: Tetrahedron Lett.43, 7769 (2002); (d) F.W.B. van Leeuwen, H. Beijleveld, H. Kooijman, A.L. Spek, W. Verboom, and D.N. Reinhoudt, J. Org. Chem. 69, 3928 (2004)

  12. The stoichiometry of 1:2 for 1,3-alternate-3 and 1:1 for cone-3 complexes are in good agreement with the stoichiometry predicted based on the conformer preferences of analogous derivatives. (a) A. Ikeda, and S. Shinkai, J. Am. Chem. Soc. 116, 3102 (1994). (b) N. Koh, K. Araki, S. Shinkai, Z. Asfari, and J. VicensTetrahedron, Lett. 36, 6095 (1995).

  13. 1H NMR spectra of titration of 3 with AgClO4, KClO4 are quite similar, showing that the nature of the counterion influences negligibly in the general features of complexation.

  14. M. Cajan P. Lhoták J. Lang H. Dvoráková I. Stibor J. Koca (2002) J. Chem. Soc. Perkin Trans. 2 1922

    Google Scholar 

  15. The percentage (%) cation extracted from neutral picrate solution into dichloromethane for Na+, K+ and Ag+ are 93, 78 and 99, respectively. The K ass for Ag+was not measured due to the chemical shift scarcely change.

  16. (a)N. Koh, T. Imada, T. Nagasaki, S. Shinkai: Tetrahedron Lett. 35, 4157 (1994); (b) A. Bilyk, A.K. Hall, J.M. Harrowfield, M.W. Hosseini, B.W. Skelton, and A.H. White: Inorg. Chem. 40, 672 (2001); (c) S. Takemoto, K. Otsuka, T. Otsuka, H. Seino, Y. Mizobe, and M. Hidai: Chem. Lett., 6 (2002); (d) T. Kajiwara, S. Yokozawa, T. Ito, N. Iki, N. Morohashi, and S. Miyano: Angew. Chem., Int. Ed.41, 2076 (2002).

  17. N. Morohashi T. Hattori K. Yokomakura C. Kabuto S. Miyano (2002) Tetrahedron Lett. 43 7769 Occurrence Handle10.1016/S0040-4039(02)01833-6

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Honjo-machi 1, Saga-shi, Saga, 840-8502, Japan

    Carol Pérez Casas & Takehiko Yamato

Authors
  1. Carol Pérez Casas
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Takehiko Yamato
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Takehiko Yamato.

Additional information

Received in final form: 26 January 2005

Rights and permissions

Reprints and permissions

About this article

Cite this article

Casas, C.P., Yamato, T. Hard–Soft Receptors, Tetrakis[(N,N-diethylaminocarbonyl)methoxy] thiacalix[4]arene Derivatives with cone and 1,3-alternate Conformation. J Incl Phenom Macrocycl Chem 53, 1–8 (2005). https://doi.org/10.1007/s10847-005-1252-3

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-005-1252-3

Keywords

Search

Navigation