Molecular receptor for binding quaternary ammonium salts and a large anion effect on the complexation

Kyu Sung Jeong, Kyu Myoung Hahn, Young Lag Cho

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33 Citations (Scopus)

Abstract

An acyclic receptor 1 with a binding cavity surrounded by electron-rich aryl surfaces has been synthesized for binding quaternary ammonium salts through cation-π interactions. The association constants of the receptor I with salts in CDCl3 depend on the anions due to the hydrogen bonds between the exchangeable protons in the receptor 1 and anions.

Original languageEnglish
Pages (from-to)3779-3782
Number of pages4
JournalTetrahedron Letters
Volume39
Issue number22
DOIs
Publication statusPublished - 1998 May 28

Bibliographical note

Funding Information:
Acknowledgement: This work was financially supported by the Basic Science Research Institute Program,

Funding Information:
Ministry of Education (Project No. BSRI-97-3422). References and Notes 1. For reviews see: a) Dougherty, D. A. Science 1996, 271,163-168. b) Ma, J. C.; Dougherty, D. A. Chem. Rev. 1997, 97, 1303-1324. 2. a) Petti, M. A.; Shepodd, T. J.; Barrans, R. E., Jr.; Dougherty, D. A. J. Am. Chem. Soc. 1988, 110, 6825-6840. b) Dhaenens, M.; Lehn, J.-M.; Fernandez, M.-J.; Vigneron, J.-P. New. J. Chem. 1991,15, 873-877. c) Cattani, A.; Cort, A. D.; Mandolini, L. J. Org. Chem. 1995, 60, 8313-8314. 3. Garel, L.; Lozach, B.; Dutasta, J.-P.; Collet, A. J. Am. Chem. Soc. 1993, 115, 11652-11653. 4. a) Shinkai, S.; Araki, K.; Matsuda, T.; Nishiyama, N.; Ikeda, H.; Takasu, I.; lwamoto, M.; J. Am. Chem. Soc. 1990, 112, 9053-9058. b) Araki, K.; Shimizu, H.; Shinkai, S. Chem. Lett. 1993, 205-208, c) De Iasi, G.; Masci, B. Tetrahedron Lett. 1993, 34, 6635-6638. d) Takeshila, M.; Nishio, S.; Shinkai, S. J. Org. Chem. 1994, 59, 4032-4034. e) Arduini, A.; MaGregor, W. M.; Paganuzzi, D.; Pochini, A.; Secchi, A.; Ugozzoli, F.; Ungaro, R. J. Chem. Soc., Perkin Trans. 2 1996, 839-846. f) Amecke, R.; B0hmer, V.; Caccipaglia, R.; Cort, A. D.; Mandolini, L. Tetrahedron 1997, 53, 4901-4908. For other calixarene analogues, see: g) Schneider, H.-J.; GUttes, D.; Schneider, U. J. Am. Chem. Soc. 1988,110, 6449-6454. h) Yanagihara, R.; Aoyama, Y. Tetrahedron Lett. 1994, 35, 9725-9728. i) Masci, B. Tetrahedron 1995, 51, 5459-5464. j) Koh, K. N.; Araki, K.; Lkeda, A.; Otsuka, H.; Shinkai, S. J. Am. Chem. Soc. 1996,118, 755-758. 5. Jeong, K.-S.; Park, J. W.; Cho, Y. L. Tetrahedron Lett. 1996, 37, 2795-2798. 6. Smith, J. G.: Dibble, P. W.; Sandborn, R. E. J. Org. Chem. 1986, 51, 3762-3768. 7. de Mendoza, J.; Nieto, P. M.; Prados, P.; Sanchez, C. Tetrahedron 1990, 46, 671-682. 8. Yield was not optimized. Physical properties of 1: Mp 124-126 °C; 1H NMR (250 MI-tz, CDC13), 8 7.36 (dd, 2H, J = 8.8, 2.5 Hz), 7.29 (s, 2H), 7.14 (s, 2H), 6.86 (d, 2H, J = 2.5 Hz), 6.74 (d, 2H, J = 8.8 Hz), 6.57 (d, 2H, J = 8.6 Hz), 6.54 (s, 2H), 6.45 (dd, 2H, J = 8.6, 2.9 Hz), 6.34 (d, 2H, J = 2.9 Hz), 5.90 (s, 2H), 3.96 (t, 4H, J = 6,7 Hz), 3.63 (d, 2H, J = 14.3 Hz), 3.37 (d, 2H, J = 14.3 Hz), 2.74 (m, 4H), 2.42 (m, 2H), 2.01-2.16 (m, 4H), 1.73-1.94 (m, 10H), 1.16-1.48 (m, 4H), 1.05 (t, 6H, J = 7.4 Hz), 0.95 (t, 6H, J = 7.2 Hz); 13C NMR (62.5 MHz, CDCI3), ~ 176.8, t52.6, 150.2, 148.1, 137,5, 137.1, 131.9, 129.8, 129.7, 127.8, 123.7, 120.9, 117.6, 117.5, 115.5, ll3.0, 71.5, 52.1, 41.4, 32.9, 31.0, 30.6, 23.0, 20.9, 18.7, 15.4, 11.l; Anal. Calcd for C54H64N208: C, 74.63; H, 7.42; N, 3.22. Found: C, 74.60; H, 7.50; N, 3.21. 9. The infrared spectrum of the receptor 1 in the presence of excess (-5 equiv) (n-Bu)4N+CY or (n-Bu)4N+Br - show a new broad band near 3200 cm -1 corresponding to the hydrogen-bonded NH groups. 10. For other anion-binding receptors, see: (a) Valiyayeettil, S; Engbersen, J. F. J.; Verhoom, W.; Reinhoudt, D. N. Angew. Chem. Int. Ed. Engl. 1993, 32, 900-901. (b) Beer, P, D, J. Chem. Soc., Chem. Comm. 1996, 689-696. 11. Association constants of the tris(thiourea) 14 with CI', Brand I" are >5.0 x 104, 3.6 x 103, and 56 M "l, respectively, in 20% DMSO-d6 in CDCI 3 at 296 K, Most of CI and Br might therefore exist as the complexes with 14 under the titration conditions, that is, 10 mM of 14 and 0.67-2.00 mM of 9"Xl in CDCI 3. 12. Mecozzi, S.; West, A. P., Jr.; Dougherty, D. A. Proc. Natl. Acad, Sci. USA 1996, 93, 10566-10571. 13. Corrors, K. A. Binding Constants: John Wiley & Sons: New York, 1984; p 24. 14. The trans receptor 19 was prepared by coupling 8 with the trans isomer of 3 (see ref. 5).

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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