Sodium binding effects on conformational exchange in a diquinone calix[4]arene

Journal of the American Chemical Society

Volumn 119, Issue 22, 1997, Pages 5222-5229

  Gómez Kaifer, Marielle ^c   Reddy, P A ^b   Gutsche, C David ^b   Echegoyen, Luis ^a  

^a UNIVERSITY OF MIAMI   (United States)

^b TEXAS CHRISTIAN UNIVERSITY   (United States)

^c NONE

Author keywords

[No Author keywords available]

Indexed keywords

CALIXARENE; SODIUM;

ARTICLE; CHEMICAL STRUCTURE; CONFORMATIONAL TRANSITION; KINETICS; NUCLEAR MAGNETIC RESONANCE;

EID: 0343097215     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja963601s     Document Type: Article

References (25)

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5. For example: (a) Ghidini, E.; Ugozzoli, F.; Ungaro, R.; Harkema, S.; El-Fadl, A. A.; Reinhoudt, D. N. J. Am. Chem. Soc. 1990, 112, 6979. (b) Takeshita, M.; Shinkai, S. Bull. Chem. Soc. Jpn. 1995, 68. 1088.
6. For example: (a) Ghidini, E.; Ugozzoli, F.; Ungaro, R.; Harkema, S.; El-Fadl, A. A.; Reinhoudt, D. N. J. Am. Chem. Soc. 1990, 112, 6979. (b) Takeshita, M.; Shinkai, S. Bull. Chem. Soc. Jpn. 1995, 68. 1088.
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20. 3CN, interconversion between the syn and anti conformers occurs at much lower temperatures. It is noticeable even at 35 °C. In contrast, Ungaro and co-workers report that the spectrum of 1 in DMSO is unchanged over the temperature range from -40 to 80°C.
21. van Loon, J.-D.; Arduini, A.; Coppi, L.; Verboom, W.; Pochini, A.; Ungaro, R.; Harkema, S.; Reinhoudt, D. N. J. Org. Chem. 1990, 55, 5639.
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23. Sandström, J. Dynamic NMR Spectroscopy; Academic Press: New York, 1982.
24. +) yields a similar pattern of NOEs, including positive effects on the neighboring methylene on the tail (3.68 ppm) and on the sidearm methylene resonance at 4.04 ppm; however, the NOE enhancement observed in the aromatic region is very weak, though an effect is noted for both the aryl and quinone protons. No enhancement was seen on the tert-butyl resonance (0.99 ppm), although the baseline in this region possibly suggests some very weak effect. In the NOE spectra of the free 1-syn conformer (not shown here), irradiation of the methyl resonance did not result in enhancement of the corresponding tert-butyl resonance.
25. -1. The high salt concentrations required to observe a substantial amount of the anti complex (unachievable in this solvent mixture), along with the continuous conversion of anti to syn in the presence of the salt, make accurate determination of the anti conformer's binding constant difficult.