Molecular Design of Crown Ethers. 4.1,2Syntheses and Selective Cation Binding of 16-Crown-5 and 19-Crown-6 Lariats

Journal of Organic Chemistry

Volumn 52, Issue 12, 1987, Pages 2420-2427

  Ouchi, Mikio ^a   Inoue, Yoshihisa ^a   Wada, Kazuhito ^a   Iketani, Shin Ichi ^a   Hakushi, Tadao ^a   Weber, Edwin ^b  

^a UNIVERSITY OF HYOGO   (Japan)

^b UNIVERSITY OF BONN   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33845281070     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00388a016     Document Type: Article

References (13)

1. Part 3: Inoue, Y.; Ouchi, M.; Hakushi, T. Bull. Chem. Soc. Jpn. 1985, 58, 525.
2. Preliminary reports: (a) Ouchi, M.; Inoue, Y.; Wada, K.; Hakushi, T. Chem. Lett, 1984, 1137. (b) Weber, E. Liebigs Ann. Chem. 1983, 770. (c) Offermann, W.; Weber, E. Chem. Ber. 1984, 117, 234.
3. (a) Himeji Institute of Technology. (b) Universitat Bonn.
4. (a) Dishong, D. M.; Diamond, C. J.; Cinaman, M. I.; Gokel, G. W. J. Am. Chem. Soc. 1983, 105, 586. (b) Schultz, R. A.; White, B. D.: Arnold, K. A.; Gokel, G. W. Angew. Chem. 1985, 107, 6659.
5. (a) Ikeda, I.; Emura, H.; Okahara, M. Bull. Chem. Soc. Jpn. 1985, 57, 1612. (b) Nakatsuji, Y.; Nakamura, T.; Okahara, M.; Dishong, D. M.; Gokel, G. W. J. Org. Chem. 1983, 48, 1237. (c) Nakatsuji, Y.; Nakamura, T.: Okahara, M. Chem. Lett. 1982, 1207.
6. Tsukube, H.; Takagi, K.; Higashiyama, T.; Hayama, N. J. Chem. Soc., Perkin Trans. 1 1986. 1033.
7. (a) Ouchi, M.; Inoue, Y.; Sakamoto, H.; Yamahira, A.; Yoshinaga, M.; Hakushi, T. J. Org. Chem. 1983, 48, 3168. (b) Ouchi, M.; Inoue, Y.; Kanzaki, T.; Hakushi, T. Angew. Chem. 1984, 49, 1408. (c) Inoue, Y.; Ouchi, M.; Hakushi, T. Bull. Chem. Soc. Jpn. 1985, 58, 525. The Kexvalues for divalent cations were reported erroneously and should read as reported here.
8. Tomoi, M.; Abe, O.; Ikeda, M.; Kihara, K.; Kakiuchi, H. Tetrahedron Lett. 1978, 3031.
9. Blicke, F. F.; Zienty, M. F. J. Am. Chem. Soc. 1941, 63, 2779.
10. (a) Weber, E. Angew. Chem. 1979, 91, 230; Angew. Chem., Int. Ed. Engl. 1979, 18, 219. (b) Weber, E. J. Org. Chem. 1982, 47, 3478.
11. Cf.: De-Jong, F.; van Zon, A.; Reinhoudt, D. N.; Torny, G. J.; Tomassen, H. P. M. Reel. Trav. Chim. Pays-Bas 1983, 102, 164.
12. As has been demonstrated by an X-ray crystallographic study of several N-pivot lariat ethers [Gandour, R. D.; Fronczek, F. R.; Gatto, V. J.; Minganti, C.; Schultz, R. A.; White, B. D.; Arnold, K. A.; Mazzocchi, D.; Miller, S. R.; Gokel, G. W. J. Am. Chem. Soc. 1986, 108, 4078], the conformation and size of the crown ring vary substantially depending upon the ligand topography, the complexed cation, and the coordination number around it. The same group and others have also shown from binding studies in homogeneous solutions that the hole-size relationship fails to explain cation selectivity in flexible macrocycles and lariat ethers. For recent papers, see: Schultz, R. A.; White, B. D.; Dishong, D. M.; Arnold, K. A.; Gokel, G. W. J. Am. Chem. Soc. 1985,107, 6659. Michaux, G.; Reisse, J. Angew. Chem. 1982, 104, 6895. On the other hand, the cation selectivity in the present case can be rationalized in terms of the size-fit concept, indicating that the concept still holds at least in the solvent extraction experiment. This may be attributed to the fairly rigid framework of 16-crown-5 as compared with larger macrocycles or to the use of solvent extraction in evaluating cation-binding ability. Alternatively, the complexation behavior of the carbon-pivot lariats might differ from that of the nitrogen-pivot lariats. A study to measure the complex stability constants in homogeneous phase is in progress using our own lariat ethers and the related crown ethers.
13. Wong, K. H.; Ng, H. L. J. Coord. Chem. 1981, 11, 49.