Novel Upper Rim Functionalizations of Calix[4]arenes using the Tscherniac-Einhorn Amidomethylation Reaction

Advanced Synthesis and Catalysis

Volumn 341, Issue 3, 1999, Pages 284-290

  Van Bommel, Kjeld J C ^a,c   Westerhof, Folke ^a   Verboom, Willem ^a   Reinhoudt, David N ^a   Hulst, Ron ^b  

^a UNIVERSITY OF TWENTE   (Netherlands)

^b UNIVERSITY OF TWENTE   (Netherlands)

^c NUCLEAR RESEARCH AND CONSULTANCY GROUP NRG   (Netherlands)

Author keywords

Amidomethylation; C C coupling; Calixarenes; Electrophilic aromatic substitutions; Synthetic methods

Indexed keywords

EID: 0347710687     PISSN: 16154150     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article

References (45)

1. For recent reviews on calix[4]arenes see: a) V. Böhmer, Angew. Chem. Int. Ed. Engl. 1995, 34, 713; b) A. Ikeda, S. Shinkai, Chem. Rev. 1997, 97, 1713
2. For recent reviews on calix[4]arenes see: a) V. Böhmer, Angew. Chem. Int. Ed. Engl. 1995, 34, 713; b) A. Ikeda, S. Shinkai, Chem. Rev. 1997, 97, 1713
3. C. D. Gutsche, J. A. Levine, J. Am. Chem. Soc. 1982, 104, 2652
4. J.-D. van Loon, A. Arduini, L. Coppi, W. Verboom, A. Pochini, R. Ungaro, S. Harkema, D. N. Reinhoudt, J. Org. Chem. 1990, 55, 5639
5. C. D. Gutsche, P. F. Pagoria, J. Org. Chem. 1985, 50, 5795
6. K. No, Y. Noh, Y. Kim, Bull. Korean Chem. Soc. 1986, 7, 442
7. A. Arduini, G. Manfredi, A. Pochini, A. R. Sicuri, R. Ungaro, J. Chem. Soc., Chem. Commun. 1991, 936
8. W. Verboom, A. Durie, R. J. M. Egberink, Z. Asfari, D. N. Reinhoudt, J. Org. Chem. 1992, 57, 1313
9. A. M. A. van Wageningen, E. Snip, W. Verboom, D. N. Reinhoudt, H. Boerrigter, Liebigs Ann./Recueil 1997, 2235
10. P. Timmerman, W. Verboom, D. N. Reinhoudt, A. Arduini, S. Grandi, A. R. Sicuri, A. Pochini, R. Ungaro, Synthesis 1994, 185
11. N. Pellizzi, A. Casnati, R. Ungaro, Chem. Commun. 1998, 2607
12. A. Casnati, M. Fochi, P. Minari, A. Pochini, M. Reggiani, R. Ungaro, D. N. Reinhoudt, Gazz. Chim. Ital. 1996, 126, 99
13. a) Houben-Weyl Methoden der Organischen Chemie, 4th ed., G. Thieme Stuttgart 1957, Vol. XI/1, 795;
14. b) Organic Reactions, John Wiley & Sons, Inc. New York-London-Sydney, 1965, Vol. 14, 63
15. V. N. Pastushok, K. Hu, J. S. Bradshaw, N. K. Dalley, A. V. Bordunov, N. G. Lukyanenko, J. Org. Chem. 1997, 62, 212
16. K. Hu, J. S. Bradshaw, V. N. Pastushok, K E. Krakowiak, N. K. Dalley, X. X. Zhang, R. M. Izatt, J. Org. Chem. 1998, 63, 4786
17. a) H. E. Zaugg, Synthesis 1984, 85;
18. b) H. E. Zaugg, Synthesis, 1984, 181;
19. c) H. E. Zaugg, Synthesis 1970, 49
20. Tetrahydroxycalix[4]arene reacts smoothly at room temperature (24 h) to afford the tetrakis(dimethylaminomethyl)-calix[4]arene. a) C. D. Gutsche, K. C. Nam, J. Am. Chem. Soc. 1998, 110, 6153; The 1,3-dimethyl ether requires 66 h reaction time in refluxing dioxane [3]; The 1,3-dibenzoate and the 1,3-diallyl ether both fail to undergo the Mannich reaction even at 140°C. b) K. C. Nam, T. H. Yoon, Bull. Korean Chem. Soc. 1993, 14, 169
21. Tetrahydroxycalix[4]arene reacts smoothly at room temperature (24 h) to afford the tetrakis(dimethylaminomethyl)-calix[4]arene. a) C. D. Gutsche, K. C. Nam, J. Am. Chem. Soc. 1998, 110, 6153; The 1,3-dimethyl ether requires 66 h reaction time in refluxing dioxane [3]; The 1,3-dibenzoate and the 1,3-diallyl ether both fail to undergo the Mannich reaction even at 140°C. b) K. C. Nam, T. H. Yoon, Bull. Korean Chem. Soc. 1993, 14, 169
22. Several strong acids were tried as solvents, however, only TFA allowed for both the reactions to take place as well as for the calix[4]arenes to stay intact. Chloroform was added for solubility reasons.
23. Alkylation of the phenol ring reduces the reactivity: A. W. Francis, J. Am. Chem. Soc. 1926, 48, 1631
24. 2Cl substituents have been used for the synthesis of a number of upper rim-bridged calix[4]arenes. a) B. R. Cameron, S. J. Loeb, J. Chem. Soc., Chem. Commun. 1996, 2003; b) D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, J. Org. Chem. 1994, 59, 3683; c) P. D. Beer, P. A. Gale, D. Hesek, Tetrahedron Lett. 1995, 36, 767; d) D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, Tetrahedron Lett. 1994, 35, 7131; ibid. J. Org. Chem. 1995, 60, 6585
25. 2Cl substituents have been used for the synthesis of a number of upper rim-bridged calix[4]arenes. a) B. R. Cameron, S. J. Loeb, J. Chem. Soc., Chem. Commun. 1996, 2003; b) D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, J. Org. Chem. 1994, 59, 3683; c) P. D. Beer, P. A. Gale, D. Hesek, Tetrahedron Lett. 1995, 36, 767; d) D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, Tetrahedron Lett. 1994, 35, 7131; ibid. J. Org. Chem. 1995, 60, 6585
26. 2Cl substituents have been used for the synthesis of a number of upper rim-bridged calix[4]arenes. a) B. R. Cameron, S. J. Loeb, J. Chem. Soc., Chem. Commun. 1996, 2003; b) D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, J. Org. Chem. 1994, 59, 3683; c) P. D. Beer, P. A. Gale, D. Hesek, Tetrahedron Lett. 1995, 36, 767; d) D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, Tetrahedron Lett. 1994, 35, 7131; ibid. J. Org. Chem. 1995, 60, 6585
27. 2Cl substituents have been used for the synthesis of a number of upper rim-bridged calix[4]arenes. a) B. R. Cameron, S. J. Loeb, J. Chem. Soc., Chem. Commun. 1996, 2003; b) D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, J. Org. Chem. 1994, 59, 3683; c) P. D. Beer, P. A. Gale, D. Hesek, Tetrahedron Lett. 1995, 36, 767; d) D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, Tetrahedron Lett. 1994, 35, 7131; ibid. J. Org. Chem. 1995, 60, 6585
28. 2Cl substituents have been used for the synthesis of a number of upper rim-bridged calix[4]arenes. a) B. R. Cameron, S. J. Loeb, J. Chem. Soc., Chem. Commun. 1996, 2003; b) D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, J. Org. Chem. 1994, 59, 3683; c) P. D. Beer, P. A. Gale, D. Hesek, Tetrahedron Lett. 1995, 36, 767; d) D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, Tetrahedron Lett. 1994, 35, 7131; ibid. J. Org. Chem. 1995, 60, 6585
29. Formylation does work for tetrakis(1-ethoxyethoxy)calix[4]-arene, but not for tetrapropoxycalix[4]arene. a) A. Arduini, S. Fanni, G. Manfredi, A. Pochini, R. Ungaro, A. R. Sicuri, F. Ugozzoli, J. Org. Chem. 1995, 60, 1448; b) P. Molenveld, J. F. J. Engbersen, H. Kooijman, A. L. Spek, D. N. Reinhoudt, J. Am. Chem. Soc. 1998, 120, 6726
30. Formylation does work for tetrakis(1-ethoxyethoxy)calix[4]-arene, but not for tetrapropoxycalix[4]arene. a) A. Arduini, S. Fanni, G. Manfredi, A. Pochini, R. Ungaro, A. R. Sicuri, F. Ugozzoli, J. Org. Chem. 1995, 60, 1448; b) P. Molenveld, J. F. J. Engbersen, H. Kooijman, A. L. Spek, D. N. Reinhoudt, J. Am. Chem. Soc. 1998, 120, 6726
31. The 1,3- and 1,2-dinitro compounds can be separated if they are tetrapropoxycalix[4]arenes, but not when they are tetrakis(1-ethoxyethoxy)calix[4]arenes. P. Timmerman, K. G. A. Nierop, E. A. Brinks, W. Verboom, F. C. J. M. van Veggel, W. P. van Hoorn, D. N. Reinhoudt, Chem. Eur. J. 1996, 2, 134
32. Depropylation under acidic conditions has been reported: Y. Morzherin, D. M. Rudkevich, W. Verboom, D. N. Reinhoudt, J. Org. Chem. 1993, 58, 7602
33. Ethoxyethoxy substituents are known to be stable under acidic conditions [22].
34. The monosubstituted product 4g, could not be separated from the calix[4]arene starting material 3b. [25] The reaction was also performed starting from several tetraalkylated calix[4]arenes, but this resulted in the formation of a mixture of mono-, di-, tri-, and tetrasubstituted products (not isolated).
35. 9; these resonances stay strongly anisochronic with no signs of collapse. For both solvents, remarkably sharp and only slowly exchanging hydroxyl signals were observed.
36. K. J. C. van Bommel, W. Verboom, D. N. Reinhoudt, manuscript in preparation.
37. 15,19]octacosa-1(25),3,5, 7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-25,26,27, 28-tetrol.
38. A. Bax, R. Freeman, J. Magn. Reson. 1981, 44, 542
39. A. Bax, D. G. Davis, J. Magn. Reson. 1985, 65, 355
40. J. Jeener, B. H. Meier, P. Bachmann, R. R. Ernst, J. Chem. Phys. 1979, 71, 4546
41. A. Bax, R. H. Griffey, B. L. Hawkins, J. Magn. Reson. 1983, 55, 301
42. D. J. States, R. A. Haberkorn, D. J. Ruben, J. Magn. Reson. 1982, 48, 286
43. A. Casnati, A. Pochini, R. Ungaro, F. Ugozzoli, F. Arnaud, S. Fanni, M.-J. Schwing, R. J. M. Egberink, F. de Jong, D. N. Reinhoudt, J. Am. Chem. Soc. 1995, 117, 2767
44. A. Ikeda, T. Tsudera, S. Shinkai, J. Org. Chem. 1997, 62, 3568
45. L. C. Groenen, J.-D. van Loon, W. Verboom, S. Harkema, A. Casnati, R. Ungaro, A. Pochini, F. Ugozzoli, D. N. Reinhoudt, J. Am. Chem. Soc. 1991, 113, 2385