Synthesis and structural analysis of mercaptothiacalix[4]arene

Abstract

The synthesis of p-tert-butyltetramercaptotetrathiacalix[4]arene 1 bearing eight sulfur atoms was achieved in high overall yield (80%); the synthetic strategy used was based on the synthesis of p-tert-butyltetrathiacalix[4]arene 2, treatment of the latter with N,N-dimethylthiacarbamoyl chloride under mild conditions, thermal transposition of the O-thiacarbamoyl into the S-thiacarbamoyl derivatives in quantitative yield and deprotection of the sulfur centres by treatment with hydrazine hydrate; the conformation of compound 1 was investigated in the solid state by X-ray diffraction on a single crystal, which revealed that compound 1 adopts the 1,3-alternate conformation.

References

1. C. D. Gutsche, Calixarenes Revisited, Monographs in Supramolecular Chemistry, no. 1, ed. J. F. Stoddart, RSC, Cambridge, 1998.
2. H. Kumagai, M. Hasegawa, S. Miyanari, Y. Sugawa, Y. Sato, T. Hori, S. Ueda, H. Kamiyama and S. Miyano, Tetrahedron Lett., 1997, 38, 3971; T. Sone, Y. Ohba, K. Moriya, H. Kumada and K. Ito, Tetrahedron Lett, 1997, 38, 10 689.
3. H. Akdas, L. Bringel, E. Graf, M. W. Hosseini, G. Mislin, J. Pansanel, A. De Cian and J. Fischer, Tetrahedron Lett., 1998, 39, 2311.
4. M. W. Hosseini, Calixarene Molecules for Separation, ed. G. J. Lumetta, ACS, Washington, DC, 1999, in press.
5. G. Mislin, E. Graf, M. W. Hosseini, A. De Cian and J. Fischer, Chem. Commun., 1998, 1345.
6. G. Mislin, E. Graf, M. W. Hosseini, A. De Cian and J. Fischer, Tetrahedron Lett., 1999, 40, 1129.
7. X. Delaigue, M. W. Hosseini, A. De Cian, J. Fischer, E. Leize, S. Kieffer and A. Van Dorsselaer, Tetrahedron Lett., 1993, 34, 3285; F. Hajek, E. Graf and M. W. Hosseini, Tetrahedron Lett., 1996, 37, 1409; F. Hajek, M. W. Hosseini, E. Graf, A. De Cian and J. Fischer, Angew. Chem., Int. Ed. Engl., 1997, 36, 1760.
8. G. Mislin, E. Graf, M. W. Hosseini, A. Bilyk, A. K. Hall, J. McB. Harrowfield, B. W. Skelton and A. H. White, Chem. Commun., 1999, 373.
9. X. Delaigue, M. W. Hosseini, N. Kyritsakas, A. De Cian and J. Fischer, J. Chem. Soc., Chem. Commun., 1995, 609.
10. C. G. Gibbs and C. D. Gutsche, J. Am. Chem. Soc., 1993, 115, 5338; C. G. Gibbs, P. K. Sujeeth, J. S. Rogers, G. G. Stanley, M. Krawiec, W. H. Watson and C. D. Gutsche, J. Org. Chem., 1995, 60, 8394.
11. X. Delaigue, J. McB. Harrowfield, M. W. Hosseini, A. De Cian, J. Fischer and N. Kyritsakas, J. Chem. Soc., Chem. Commun., 1994, 1579.
12. P. RaoM. W. HosseiniA. De CianJ. FischerEur. J. Inorg. Chem. 1999, submitted..
13. X. Delaigue and M. W. Hosseini, Tetrahedron Lett., 1993, 34, 8111.
14. M. S. Newman and H. A. Karnes, J. Org. Chem., 1966, 31, 3980; Y. Ting, W. Verboom, L. G. Groenen, J.-D. van Loon and D. N. Reinhoudt, J. Chem. Soc., Chem. Commun., 1990, 1432.
15. N. Iki, F. Narumi, T. Fujimoto, N. Morohashi and S. Miyano, J. Chem. Soc., Perkin Trans. 2, 1998, 2745; H. Akdas, G. Mislin, E. Graf, M. W. Hosseini, A. De Cian and J. Fischer, Tetrahedron Lett., 1999, 40, 2113.