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Synlett 2014; 25(08): 1181-1185
DOI: 10.1055/s-0033-1341058
DOI: 10.1055/s-0033-1341058
letter
Design and Synthesis of a New Kind of Cavitand: Tetrapyrazolylcalix[4]arenes and Their Supramolecular Assemblies
Further Information
Publication History
Received: 21 December 2013
Accepted after revision: 02 March 2014
Publication Date:
07 April 2014 (online)
Abstract
Two novel calix[4]arene-based tetrapyrazolyl cavitands with different cavity size were synthesized by multistep reactions. In the solid state, one of the cavitands forms an infinite chain by intermolecular hydrogen bonding. The other cavitand undergoes coordination self-assembly with dimetal corners to form a supramolecular cage.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References
- 1a Lehn J.-M. Supramolecular Chemistry: Concepts and Perspectives. VCH; Weinheim: 1995
- 1b Comprehensive Supramolecular Chemistry . Atwood JL, Davies JE. D, Macnicol DD, Vögtle F. Pergamon; Oxford: 1996
- 1c Issacs L, Chin DN, Bowden N, Xia YN, Whiteside GM In Supramolecular Materials and Technologies . Reinhoudt DN. Wiley; Chichester: 1999. Chap. 1, 1
- 1d Steed JW, Atwood JL. Supramolecular Chemistry . Wiley; Chichester: 2000
- 1e Supramolecular Chemistry: From Molecules to Nanomaterials. Gale PA, Steed JW. Wiley; Chichester: 2012
- 2 Cram DJ, Cram MJ. Container Molecules and Their Guests . Royal Society of Chemistry; Cambridge: 1994
- 3a Gutsche CD. Calixarenes . Royal Society of Chemistry; Cambridge: 2008
- 3b Calixarenes in the Nanoworld . Vicens J, Harrowfield J, Baklouti L. Springer; Dordrecht: 2007
- 4a Thomas H, Rudkevich DM, Rebek JJr. Nature 1998; 394: 764
- 4b Trembleau L, Rebek JJr. Science 2003; 301: 1219
- 4c Hof F, Craig SL, Nuckolls C, Rebek JJr. Angew. Chem. Int. Ed. 2002; 41: 1488
- 5a Elguero J In Comprehensive Heterocyclic Chemistry . Vol. 5. Katritzky A, Rees CW. Pergamon; Oxford: 1984: 277
- 5b Elguero J In Comprehensive Heterocyclic Chemistry II. Vol. 3. Katrizky A, Rees CW, Scriven EF. V. Elsevier; Oxford: 1996: 3
- 6a 1,3-Dipolar Cycloaddition Chemistry . Vol. 1. Padwa A. Wiley; New York: 1984
- 6b Ramirez F, Bhatia SB, Patwardhan AV, Smith CP. J. Org. Chem. 1967; 32: 3547
- 7a La Monica G, Ardizzoia GA. Prog. Inorg. Chem. 1997; 46: 151
- 7b Trofimenko S. Prog. Inorg. Chem. 1986; 34: 115
- 7c Trofimenko S. Chem. Rev. 1972; 72: 497
- 8a Tong J, Yu S.-Y, Li H. Chem. Commun. 2012; 48: 5343
- 8b Yu S.-Y, Jiao Q, Li S.-H, Huang H.-P, Li Y.-Z, Sei Y, Yamaguchi K. Org. Lett. 2007; 9: 1379
- 8c Yu S.-Y, Huang H.-P, Li S.-H, Jiao Q, Li Y.-Z, Wu B, Sei Y, Yamaguchi K, Pan Y.-J, Ma H.-W. Inorg. Chem. 2005; 44: 9471
- 8d Qin L, Yao L.-Y, Yu S.-Y. Inorg. Chem. 2011; 51: 2443
- 8e Yao L.-Y, Yu Z.-S, Qin L, Li Y.-Z, Qin Y, Yu S.-Y. Dalton Trans. 2013; 3447
- 9 5,11,17,23-Tetrakis(3,5-dimethyl-1H-pyrazol-4-yl)-25,26,27,28-tetrapropoxycalix[4]arene (1) White powder; yield: 546 mg (85%); mp 285–289 °C; 1H NMR (400 MHz, DMSO-d 6, 20 °C): δ = 11.86 (s, 4 H, HN-pyrazole), 6.64 (s, 8 H, H-Ar), 4.44 and 3.24 (d, Ј = 12.1 Hz, 8 H, Ar-CH 2-Ar), 3.82 (t, Ј = 8.6 Hz, 8 H, ArOCH2 CH2CH3), 2.03 and 1.62 (s, 24 H, pyrazole-CH 3 ), 1.96 (ψ-sextet, 8 H, ArOCH2 CH2 CH3), 0.98 (t, J = 8.4 Hz, 12 H, ArOCH2CH2 CH3 ); 13C NMR (100 MHz, DMSO-d 6, 25 °C): δ = 135.6, 134.3, 128.9, 118.41, 79.26, 56.59, 23.31, 18.63, 10.52; MS (MALDI–TOF, MeOH): m/z: calcd for [M + Na]+ 991.56; found 991.6. 5,11,17,23-Tetrakis[4-(3,5-dimethyl-1H-pyrazol-4-yl)phenyl]-25,26,27,28-tetrapropoxycalix[4]arene (2) White power; yield: 55 mg (75%); mp 233–240 °C; 1H NMR (400 MHz, DMSO-d 6, 25 °C): δ = 12.19 (s, 4 H, HN-pyrazole), 7.34 (s, J = 8.8 Hz, 8 H, phenyl-H), 7.01–7.08 (d, J = 8.4 Hz, 8 H, phenyl-H), 6.98 (s, 8 H, calixarene-Ar-H), 4.51 and 3.43 (d, J = 7.8 Hz, 8 H, ArCH2 Ar), 3.98 (d, J = 12.8 Hz, 8 H, ArOCH2 CH2CH3), 2.17 (s, 24 H, pyrazole-CH3 ), 1.97–2.01 (4-sextet, J = 8.0 Hz, 8 H, ArOCH2 CH2 CH3), 1.00 (t, J = 7.4 Hz, 12 H, ArOCH2CH2 CH3 ). 13C NMR (100 MHz, CDCl3, 25 °C): δ = 157.32, 146.72, 135.55, 134.46, 133.56, 129.92, 127.26, 126.74, 31.33, 23.34, 10.38. MS (MALDI–TOF, MeOH–DMSO): m/z: calcd for [M + H2O + H+]: 1291.7; found: 1290.1. Anal Calcd for C84H88N8O4·2H2O: C, 77.03; H, 7.08; N, 8.56. Found: C, 77.11, H, 7.06; N, 8.52.
- 10 Crystallographic data for compound 1 have been deposited with the accession number CCDC 928591, and can be obtained free of charge from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44(1223)336033; E-mail: deposit@ccdc.cam.ac.uk; Web site: www.ccdc.cam.ac.uk/conts/retrieving.html.