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Synlett 2006(6): 924-926  
DOI: 10.1055/s-2006-933140
LETTER
© Georg Thieme Verlag Stuttgart · New York

The Hiratani-Double-Claisen Rearrangement as a Key Step in the Preparation of Sequential Bis(8-hydroxyquinoline) Ligands

Markus Albrecht*a, Olga Osetskaa, Roland Fröhlichb
a Institut für Organische Chemie der RWTH Aachen, Landoltweg 1, 52074 Aachen, Germany
b Organisch-Chemisches Institut der Universität Münster, Corrensstraße 40, 49148 Münster, Germany
Fax: +49(241)8092385; e-Mail: markus.albrecht@oc.rwth-aachen.de;
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Publication History

Received 5 January 2006
Publication Date:
14 March 2006 (online)

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Abstract

Symmetric and sequential isobutenylidene-bridged bis-(8-hydroxyquinoline)s are prepared by application of the Hiratani-double-Claisen rearrangement as a key step in the reaction sequence. The formation of a dinuclear helicate-type zinc(II) complex is also described.

Keywords

8-hydroxyquinoline - complexes - Claisen rearrangement - self-assembly - supramolecular chemistry

    References and Notes

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9

Characterization of 5: 1H NMR (300 MHz, CDCl3): δ = 8.22 (d, J = 8.2 Hz, 2 H), 7.69 (t, J = 8.2 Hz, 2 H), 7.67 (d, J = 8.2 Hz, 2 H), 7.44 (d, J = 8.2 Hz, 2 H), 7.40 (br d, J = 7.7 Hz, 2 H), 5.59 (s, 2 H), 5.09 (s, 4 H). MS (EI): m/z = 392 [M + H]+. Characterization of 6: 1H NMR (300 MHz, CDCl3): δ = 8.28 (d, J = 8.4 Hz, 1 H), 7.62 (t, J = 8.2 Hz, 1 H), 7.48 (d, J = 8.2 Hz, 1 H), 7.40 (d, J = 8.4 Hz, 1 H), 7.23 (br d, J = 7.4 Hz, 1 H), 5.49 (s, 1 H), 5.48 (s, 1 H), 4.97 (s, 2 H), 4.33 (s, 2 H). MS (EI): m/z = 223 [M + H]+. Characterization of 7: 1H NMR (300 MHz, CDCl3): δ = 10.07 (s, 2 H), 8.50 (d, J = 8.5 Hz, 2 H), 7.92 (d, J = 8.2 Hz, 2 H), 7.51 (d, J = 8.2 Hz, 2 H), 7.44 (d, J = 8.5 Hz, 2 H), 4.66 (s, 2 H), 3.53 (s, 4 H). Characterization of 8: 1H NMR (300 MHz, DMSO-d 6): δ = 8.39 (d, J = 8.7 Hz, 2 H), 8.14 (d, J = 8.4 Hz, 2 H), 7.51 (d, J = 8.24, 2 H), 7.44 (d, J = 8.5 Hz, 2 H), 4.66 (s, 2 H), 3.53 (s, 4 H). MS (EI): m/z = 427.3 [M + H]+.

10

Characterization of 9: 1H NMR (300 MHz, CDCl3): δ = 8.92 (dd, J = 8.4, 1.8 Hz, 1 H), 8.22 (d, J = 8.5 Hz, 1 H), 8.12 (dd, J = 8.2, 1.8 Hz, 1 H), 7.69 (d, J = 8.3 Hz, 1 H), 7.40 (m, 7 H), 5.58 (s, 2 H), 5.11 (s, 2 H), 5.05 (s, 2 H). Characterization of 10: 1H NMR (300 MHz, CDCl3): δ = 8.75 (dd, J = 4.4, 1.6 Hz, 1 H), 8.24 (d, J = 8.3 Hz, 1 H), 8.10 (dd, J = 8.2, 1.4 Hz, 1 H), 7.94 (br s, 1 H), 7.65 (d, J = 8.6 Hz, 1 H), 7.57 (d, J = 8.6 Hz, 1 H), 7.30 (m, 4 H), 4.91 (s, 1 H), 4.86 (s, 1 H), 3.67 (s, 2 H), 3.65 (s, 2 H). Characterization of 11-H3: Mp 136 °C. 1H NMR (300 MHz, DMSO-d 6): δ = 8.81 (dd, J = 4.2, 1.7 Hz, 1 H), 8.48 (d, J = 8.4 Hz, 1 H), 8.27 (dd, J = 8.4, 1.5 Hz, 1 H), 8.08 (d, J = 8.2 Hz, 1 H), 7.48 (m, 3 H), 7.35 (s, 2 H), 4.70 (s, 2 H), 3.58 (s, 2 H), 3.55 (s, 2 H). MS (ESI+): m/z = 387 [M + H]+. Anal. Calcd for C23H18O4N2·0.66H2O: C, 69.34; H, 4.89; N, 7.03. Found: C, 69.21; H, 4.76; N, 6.92.

11

Characterization of K2[(11)2Zn2]: 1H NMR (300 MHz, DMSO-d 6): δ = 8.45 (d, J = 8.2 Hz, 1 H), 8.34 (m, 1 H), 7.96 (m, 2 H), 7.53 (d, J = 8.2 Hz, 1 H), 7.36 (m, 2 H), 6.92 (m, 2 H), 4.81 (s, 1 H). 4.18 (s, 1 H); the signals of the benzylic protons are hidden under the solvent and water peaks. MS (ESI+): m/z = 899 [M + H]+. Anal. Calcd for C46H30O8N4Zn2K2·5H2O: C, 51.84; H, 3.78; N, 5.26. Found: C, 51.82; H, 3.37; N, 4.95.