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The Synthesis of Sulfo Derivatives of Calix[4]arenes Yury Yu. Morzherin Ekaterinburg Department of Technology for Organic Synthesis The Urals State Technical.

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Presentation on theme: "The Synthesis of Sulfo Derivatives of Calix[4]arenes Yury Yu. Morzherin Ekaterinburg Department of Technology for Organic Synthesis The Urals State Technical."— Presentation transcript:

1 The Synthesis of Sulfo Derivatives of Calix[4]arenes Yury Yu. Morzherin Ekaterinburg Department of Technology for Organic Synthesis The Urals State Technical University – UPI

2 Sulfo Derivatives of Calix[4]arenes Shinkai S.; Mori S.; Sone T.; Manade O. Tetrahedron Lett. 1984, 25, 5315 Scharff J.; Mahjoubi M. J.New.Chem. 1991, 15, 883

3 Water-soluble Receptors S.Shinkai, K.Araki, M. Kubota, T. Arimura, T.Matsuda, J.Org.Chem. 1991, 56, 295 for Cu 2+, Zn 2+, Ni 2+, UO 2 2+ G.Arena, A.Contino, F.Gulino, A.Margi, D.Sciotto, R.Ungaro, Tetrahedron Lett. 2000, 41, 9327 for acetonitrile, acetone

4 Chlorosulfonylated of Calix[4]arene Morzherin, Yu.; Rudkevich, D.M.; Verboom, W.; Reinhoudt, D.N. J.Org.Chem. 1993, 58, 7602 for R = Me, Et, Pr

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6 The Synthesis of Anion Receptors

7 Anion Receptors Cl - HSO 4 - HNO 3 - ClO 4 - K ass = 1250 103400 513 <1 Morzherin, Yu.; Rudkevich, D.M.; Verboom, W.; Reinhoudt, D.N. J.Org.Chem. 1993, 58, 7602 Cl - HSO 4 - HNO 3 - ClO 4 - K ass = 360 970 240 <1

8 Synthesis of p-sulfonatocalix[4]arenes

9 SO 3 (30-40%) H 2 SO 4 Sodium free H 2 SO 4 SO 3 (30-40%) Sodium free

10 H 2 SO 4 SO 3 (30-40%)

11 Synthesis of ditopic receptors

12 The NMR Determination of K ass

13 K ass, M -1 in CH 3 CN-H 2 O R 1 = i-Pr t-Bu Cl - HSO 4 - 180 650 72 134 R 1 = i-Pr t-Bu Cl - HSO 4 - 1270 8020 970 4000

14 Acknowledgment Prof. David Reinhoudt Dr. Wim Verboom Dr. Dmitry Rudkevich The authors also thank the Russian Foundation for Basic Research (Grant 01-03-96431a) Research team A.I. Matern, PhD T.V. Glukhareva, PhD M.F. Kosterina, PhD-student


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