Isolation, characterization, and conformational characteristics of p- tert-butylcalix[9 - 20]arenes

Journal of the American Chemical Society

Volumn 121, Issue 17, 1999, Pages 4136-4146

  Stewart, Donald R ^a   Gutsche, C David ^a  

^a TEXAS CHRISTIAN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CALIXARENE;

ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL REACTION; CONFORMATIONAL TRANSITION; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; HYDROGEN BOND; POLYMERIZATION; PURIFICATION; SOLUBILITY;

EID: 0033526332     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983964n     Document Type: Article

References (45)

1. Paper 52 in the series Calixarenes. For paper 51 cf.: Sharma, S. K.; Gutsche, C. D. J. Org. Chem. 1999, 64, In press.
2. For extensive reviews cf.: (a) Gutsche, C. D. Calixarenes Revisited. In Monographs in Supramolecular Chemistry; Stoddart, J. F., Ed.; Royal Society of Chemistry: London, 1998.
3. For extensive reviews cf.: (a) Gutsche, C. D. Calixarenes Revisited. In Monographs in Supramolecular Chemistry; Stoddart, J. F., Ed.; Royal Society of Chemistry: London, 1998. (b) McKervey, M. A.; Schwing-Weill, M.-J.; Arnaud-Neu, F. Cation Binding by Calixarenes. In Comprehensive Supramolecular Chemistry; Gokel, G., Ed.; Pergamon Press: New York, 1996; Vol. 1, p 537-603. (c) Pochini, A.; Ungaro, R. Calixarenes and Related Hosts. In Comprehensive Supramolecular Chemistry; Vögtle, F., Ed.; Pergamon Press: New York, 1996; Vol. 2, pp 103-142. (d) Böhmer, V. Calixarenes, Macrocyclic with (Almost) Unlimited Possibilities. Angew. Chem. Int. Ed. Engl. 1995, 34, 713-745. (e) Gutsche, C. D. Calixarenes. In Monographs in Supramolecular Chemistry; Stoddart, J. F., Ed.; Royal Society of Chemistry: London, 1989.
4. For extensive reviews cf.: (a) Gutsche, C. D. Calixarenes Revisited. In Monographs in Supramolecular Chemistry; Stoddart, J. F., Ed.; Royal Society of Chemistry: London, 1998. (b) McKervey, M. A.; Schwing-Weill, M.-J.; Arnaud-Neu, F. Cation Binding by Calixarenes. In Comprehensive Supramolecular Chemistry; Gokel, G., Ed.; Pergamon Press: New York, 1996; Vol. 1, p 537-603. (c) Pochini, A.; Ungaro, R. Calixarenes and Related Hosts. In Comprehensive Supramolecular Chemistry; Vögtle, F., Ed.; Pergamon Press: New York, 1996; Vol. 2, pp 103-142. (d) Böhmer, V. Calixarenes, Macrocyclic with (Almost) Unlimited Possibilities. Angew. Chem. Int. Ed. Engl. 1995, 34, 713-745. (e) Gutsche, C. D. Calixarenes. In Monographs in Supramolecular Chemistry; Stoddart, J. F., Ed.; Royal Society of Chemistry: London, 1989.
5. For extensive reviews cf.: (a) Gutsche, C. D. Calixarenes Revisited. In Monographs in Supramolecular Chemistry; Stoddart, J. F., Ed.; Royal Society of Chemistry: London, 1998. (b) McKervey, M. A.; Schwing-Weill, M.-J.; Arnaud-Neu, F. Cation Binding by Calixarenes. In Comprehensive Supramolecular Chemistry; Gokel, G., Ed.; Pergamon Press: New York, 1996; Vol. 1, p 537-603. (c) Pochini, A.; Ungaro, R. Calixarenes and Related Hosts. In Comprehensive Supramolecular Chemistry; Vögtle, F., Ed.; Pergamon Press: New York, 1996; Vol. 2, pp 103-142. (d) Böhmer, V. Calixarenes, Macrocyclic with (Almost) Unlimited Possibilities. Angew. Chem. Int. Ed. Engl. 1995, 34, 713-745. (e) Gutsche, C. D. Calixarenes. In Monographs in Supramolecular Chemistry; Stoddart, J. F., Ed.; Royal Society of Chemistry: London, 1989.
6. For extensive reviews cf.: (a) Gutsche, C. D. Calixarenes Revisited. In Monographs in Supramolecular Chemistry; Stoddart, J. F., Ed.; Royal Society of Chemistry: London, 1998. (b) McKervey, M. A.; Schwing-Weill, M.-J.; Arnaud-Neu, F. Cation Binding by Calixarenes. In Comprehensive Supramolecular Chemistry; Gokel, G., Ed.; Pergamon Press: New York, 1996; Vol. 1, p 537-603. (c) Pochini, A.; Ungaro, R. Calixarenes and Related Hosts. In Comprehensive Supramolecular Chemistry; Vögtle, F., Ed.; Pergamon Press: New York, 1996; Vol. 2, pp 103-142. (d) Böhmer, V. Calixarenes, Macrocyclic with (Almost) Unlimited Possibilities. Angew. Chem. Int. Ed. Engl. 1995, 34, 713-745. (e) Gutsche, C. D. Calixarenes. In Monographs in Supramolecular Chemistry; Stoddart, J. F., Ed.; Royal Society of Chemistry: London, 1989.
7. Gutsche, C. D.; Rogers, J. S.; Stewart, D. R.; See, K.-A. Pure Appl. Chem. 1990, 62, 485. Stewart, D. R.; Gutsche, C. D. Third International Calixarene Conference; Fort Worth, TX, 1995, Abstract P-42. Gutsche, C. D.; Gibbs, C. G.; Sharma, S. K.; Stewart, D. R.; Wang, J.; Xie, D. Fourth International Conference on Calixarenes, Parma, 1997; Abstract IL1.
8. Gutsche, C. D.; Rogers, J. S.; Stewart, D. R.; See, K.-A. Pure Appl. Chem. 1990, 62, 485. Stewart, D. R.; Gutsche, C. D. Third International Calixarene Conference; Fort Worth, TX, 1995, Abstract P-42. Gutsche, C. D.; Gibbs, C. G.; Sharma, S. K.; Stewart, D. R.; Wang, J.; Xie, D. Fourth International Conference on Calixarenes, Parma, 1997; Abstract IL1.
9. Gutsche, C. D.; Rogers, J. S.; Stewart, D. R.; See, K.-A. Pure Appl. Chem. 1990, 62, 485. Stewart, D. R.; Gutsche, C. D. Third International Calixarene Conference; Fort Worth, TX, 1995, Abstract P-42. Gutsche, C. D.; Gibbs, C. G.; Sharma, S. K.; Stewart, D. R.; Wang, J.; Xie, D. Fourth International Conference on Calixarenes, Parma, 1997; Abstract IL1.
10. The calixarenes discussed in this paper, all of which are p-tert-butyl substituted, are identified in abbreviated fashion by a bold, bracketed numeral that indicates the number of p-tert-butylaryl residues in the cyclic array.
11. Gutsche, C. D.; Iqbal, M. Org. Synth. 1990, 68, 234.
12. Gutsche, C. D.; Dhawan, B.; Leonis, M.; Stewart, D. R. Org. Synth. 1990, 68, 238.
13. Munch, J. H.; Gutsche, C. D.Org. Syntheses 1990, 68, 243.
14. Stewart, D. R; Gutsche, C. D. Org. Prep. Proc. Intl. 1993, 25, 137.
15. 6 with a linear trimer. Although their melting points differ substantially from those reported in the present paper, other data are in good agreement.
16. Ludwig and Bailie detected ca. 5% of calixarenes [4]-[8] in the product mixture that consisted mainly of linear oligomers: Ludwig, L. B.; Bailie, A. G., Jr. Anal. Chem. 1986, 58, 2069.
17. p-tert-Butylcalix[7]arene ([7]) can be isolated from the acid-catalyzed reaction mixture in yields as high as 25%, Vocanson et al. report the formation of [7] in 16.8% yield from a base-induced reaction: Vocanson, F.; Lamartine, R.; Lanteri, P.; Longeray, R.; Gauvrit, J. Y. New J. Chem. 1995, 19, 825.
18. A third HPLC separation using a chemically bonded C-60 stationary phase has been reported (Saito, Y.; Ohta, H.; Terasaki, H.; Katoh, Y.; Nagashima, H.; Jinno, K.; Itoh, K.; Trengove, R. D.; Harrowfield, J.; Li, S. F. Y. HRC-J. High Res. Chromatogr. 1996, 19, 475).
19. Ludwig, F. J.; Bailie, A. G., Jr. Anal. Chem. 1984, 50, 2081.
20. Snyder, L. R.; Glajch, J. L.; Kirkland, J. J. Practical HPLC Method Development; John Wiley & Sons: New York, 1988, p 37.
21. In some of the HPLC assays small, broad peaks beyond [20] were observed, presumably indicating the presence of even larger calixarenes.
22. Acetic acid is added to suppress the ionization of the calixarenes, which are rather strong acids.
23. Vocanson, F.; Lamartine, R.; Duchamp, C.; Regnouf de Vains, J. B. Chromatographia 1995, 41, 204.
24. Casiraghi, G.; Cornia, M.; Ricci, G.; Balduzzi, G.; Casnati, G. Makromol. Chem. 1983, 184, 1363.
25. The isolated yield of 0.2% for [20] is for a reaction ran at 50% (w/v). The isolated yield of [20] can be increased to at least 0.5% by employing the most concentrated reaction conditions.
26. In EtOAc/hexane [20] elutes before [18], [16], [14], [15], [12], and [19], respectively.
27. 1H NMR spectrum of the compound was measured in the presence of a chiral shift reagent. However, the shift reagent, just like pyridine, changes the spectrum to the pattern shown in Figure 3 (bottom), and no doubling of resonances was observed. Thus, although casting doubt on the trefoil structure, the results are somewhat inconclusive.
28. 2H no reaction was observed, while with the ion-exchange resin Amberlyst-15 the reaction proceeded mainly to give short hydroxymethylated linear oligomers along with trace amounts of the smallest calixarenes ([4] was isolated from the reaction mixture).
29. 1H NMR spectrum of the noncalixarene fraction of an acid-catalyzed reaction mixture in which toluene was used as the solvent. These singlets were interpreted as arising from the methyl protons of the toluene residues in the linear oligomers.
30. Linear oligomers with two and three residues evolve similarly, and p-tert-butylphenol decreases in a pseudo-first-order fashion during the first 60 min of the reaction.
31. Fragmentation/recombination has been shown to play a dominant role in the base-induced condensation of p-tert-butylphenol and formaldehyde (Dhawan, B.; Chen, S.-I.; Gutsche, C. D. Makromol. Chem. 1987, 188, 921 and ref 2a) and the acid-catalyzed preparation of calixrescorcarenes (ref 2e, p 33).
32. In the aliquot study no oligomers with hydroxymethyl groups were detected.
33. For nomenclature cf. p 7 of ref 2a.
34. See p 60 of ref 2a for an enumeration of the conformers of calix-[6]arenes
35. Kämmerer, H.; Happel, G.; Caesar, F. Makromol. Chem. 1972, 162, 179. Happel G.; Mathiasch, B.; Kämmerer, H. Makromol. Chem. 1975, 176, 3317.
36. Kämmerer, H.; Happel, G.; Caesar, F. Makromol. Chem. 1972, 162, 179. Happel G.; Mathiasch, B.; Kämmerer, H. Makromol. Chem. 1975, 176, 3317.
37. Kurland, R. S.; Rubin, N. B.; Wise, W. B. J. Chem. Phys. 1964, 40, 2426.
38. Gutsche, C. D.; Bauer, L. J. J. Am. Chem. Soc. 1985, 107, 6052.
39. Kämmerer, H.; Happel, G. Makromol. Chem. 1980, 181, 2049. Kämmerer, H.; Happel, G. Monaatsh. Chem. 1981, 112, 759. Kämmerer, H.; Happel, G.; Mathiasch, B. Monastsh. Chem. 1981, 182, 1685. Stewart, D. R.; Krawiec, M.; Kashyap, R. P.; Watson, W. H.; Gutsche, C. D. J. Am. Chem. Soc. 1995, 117, 586.
40. Kämmerer, H.; Happel, G. Makromol. Chem. 1980, 181, 2049. Kämmerer, H.; Happel, G. Monaatsh. Chem. 1981, 112, 759. Kämmerer, H.; Happel, G.; Mathiasch, B. Monastsh. Chem. 1981, 182, 1685. Stewart, D. R.; Krawiec, M.; Kashyap, R. P.; Watson, W. H.; Gutsche, C. D. J. Am. Chem. Soc. 1995, 117, 586.
41. Kämmerer, H.; Happel, G. Makromol. Chem. 1980, 181, 2049. Kämmerer, H.; Happel, G. Monaatsh. Chem. 1981, 112, 759. Kämmerer, H.; Happel, G.; Mathiasch, B. Monastsh. Chem. 1981, 182, 1685. Stewart, D. R.; Krawiec, M.; Kashyap, R. P.; Watson, W. H.; Gutsche, C. D. J. Am. Chem. Soc. 1995, 117, 586.
42. Kämmerer, H.; Happel, G. Makromol. Chem. 1980, 181, 2049. Kämmerer, H.; Happel, G. Monaatsh. Chem. 1981, 112, 759. Kämmerer, H.; Happel, G.; Mathiasch, B. Monastsh. Chem. 1981, 182, 1685. Stewart, D. R.; Krawiec, M.; Kashyap, R. P.; Watson, W. H.; Gutsche, C. D. J. Am. Chem. Soc. 1995, 117, 586.
43. 2Ar methylene protons, as illustrated below for one such envelope: (matrix presented)
44. Gutsche, C. D.; Gutsche, A. E.; Karaulov, A. I. J. Incl. Phenom. 1985, 3, 447.
45. Gutsche, C. D.; Bauer, L. J. Tetrahedron Lett. 1981, 22, 4763