Download PDF
Synlett 2014; 25(08): 1181-1185
DOI: 10.1055/s-0033-1341058
letter
© Georg Thieme Verlag Stuttgart · New York

Design and Synthesis of a New Kind of Cavitand: Tetrapyrazolylcalix[4]arenes and Their Supramolecular Assemblies

Xuan-Feng Jiang
a   Laboratory for Self-Assembly Chemistry, Department of Chemistry, Renmin University of China, Beijing 100872, P. R. of China   Fax: +86(10)625166   Email: yusy@ruc.edu.cn
,
Yu-Xin Cui
b   Medical and Health Analysis Center, Peking University, Beijing 100083, P. R. of China
,
Shu-Yan Yu*
a   Laboratory for Self-Assembly Chemistry, Department of Chemistry, Renmin University of China, Beijing 100872, P. R. of China   Fax: +86(10)625166   Email: yusy@ruc.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 21 December 2013

Accepted after revision: 02 March 2014

Publication Date:
07 April 2014 (online)

    Permissions and Reprints All articles of this category


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.

Key words

cavitands - calixarenes - hydrogen bonding - self-assembly - macrocycles

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
      CrossrefGoogle Scholar
    • 1b Comprehensive Supramolecular Chemistry . Atwood JL, Davies JE. D, Macnicol DD, Vögtle F. Pergamon; Oxford: 1996
      Google Scholar
    • 1c Issacs L, Chin DN, Bowden N, Xia YN, Whiteside GM In Supramolecular Materials and Technologies . Reinhoudt DN. Wiley; Chichester: 1999. Chap. 1, 1
      Google Scholar
    • 1d Steed JW, Atwood JL. Supramolecular Chemistry . Wiley; Chichester: 2000
      CrossrefGoogle Scholar
    • 1e Supramolecular Chemistry: From Molecules to Nanomaterials. Gale PA, Steed JW. Wiley; Chichester: 2012
      CrossrefGoogle Scholar
  • 2 Cram DJ, Cram MJ. Container Molecules and Their Guests . Royal Society of Chemistry; Cambridge: 1994
    Google Scholar
    • 3a Gutsche CD. Calixarenes . Royal Society of Chemistry; Cambridge: 2008
      Google Scholar
    • 3b Calixarenes in the Nanoworld . Vicens J, Harrowfield J, Baklouti L. Springer; Dordrecht: 2007
      CrossrefGoogle Scholar
    • 4a Thomas H, Rudkevich DM, Rebek JJr. Nature 1998; 394: 764
      Crossref
    • 4b Trembleau L, Rebek JJr. Science 2003; 301: 1219
      Crossref
    • 4c Hof F, Craig SL, Nuckolls C, Rebek JJr. Angew. Chem. Int. Ed. 2002; 41: 1488
      CrossrefPubMed
    • 5a Elguero J In Comprehensive Heterocyclic Chemistry . Vol. 5. Katritzky A, Rees CW. Pergamon; Oxford: 1984: 277
      Google Scholar
    • 5b Elguero J In Comprehensive Heterocyclic Chemistry II. Vol. 3. Katrizky A, Rees CW, Scriven EF. V. Elsevier; Oxford: 1996: 3
      Google Scholar
    • 6a 1,3-Dipolar Cycloaddition Chemistry . Vol. 1. Padwa A. Wiley; New York: 1984
      Google Scholar
    • 6b Ramirez F, Bhatia SB, Patwardhan AV, Smith CP. J. Org. Chem. 1967; 32: 3547
      Crossref
    • 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
      Crossref
    • 8a Tong J, Yu S.-Y, Li H. Chem. Commun. 2012; 48: 5343
      Crossref
    • 8b Yu S.-Y, Jiao Q, Li S.-H, Huang H.-P, Li Y.-Z, Sei Y, Yamaguchi K. Org. Lett. 2007; 9: 1379
      Crossref
    • 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
      Crossref
    • 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.