Synlett 2004(13): 2385-2387  
DOI: 10.1055/s-2004-832817
LETTER
© Georg Thieme Verlag Stuttgart · New York

New Molecular Clips from Diphenylglycoluril and Catechol: Preparation, Structure and Conformation Studies, Binding Properties

Qing-Sheng Liu, Shu-Ling Gong, Yan Ding, Yuan-Yin Chen*, Xiao-Jun Wu
Department of Chemistry, Wuhan University, Wuhan 430072, P. R. China
Fax: +86(27)87647617; e-Mail: yychen@whu.edu.cn;
Further Information

Publication History

Received 15 July 2004
Publication Date:
24 September 2004 (online)

Abstract

A new molecular clip and its two alkylated derivatives, which are soluble in most of organic solvents, were prepared from hydroxymethylated diphenylglycoluril and catechol. The structure and conformation of these new clips were studied. Their binding properties for dihydroxybenzene were also studied with the aid of 1H NMR titration.

    References

  • 1 Smeets JWH. Sijbesma RP. Niele FGM. Spek AL. Smeets WJJ. Nolte RJM. J. Am. Chem. Soc.  1987,  109:  928 
  • 2 Creaven BS. Gallagher JF. McDongh JP. McGinley J. Murray BA. Whelan GS. Tetrahedron  2004,  60:  137 
  • 3 Philp D. Stoddart JF. Angew. Chem., Int. Ed. Engl.  1996,  35:  1155 
  • 4 Lehn JM. In Superamolecular Chemistry   VCH; New York: 1995. 
  • 5 Elemans JAAW. Slangen RRJ. Rowan AE. Nolte RJM. J. Org. Chem.  2003,  68:  9040 
  • 6 Lutzen A. Starnes SD. Rudkevich DM. Rebek J. Tetrahedron Lett.  2000,  41:  3777 
  • 7 Sijbesma RP. Kentgens APM. Lutz ETG. Maas JH. Nolte RJM. J. Am. Chem. Soc.  1993,  115:  8999 
  • 9 iii) has been obtained by Nolte et al. by using SnCl4 as a catalyst, the 1H NMR spectrum of 3b show much difference form that of iii). See: Sijbesma RP. Nolte RJM. Recl. Trav. Chim. Pays-Bas  1993,  112:  643 
  • 10 Isaacs L. Witt D. Lagona J. Org. Lett.  2001,  3:  3221 
  • 11 Wu A. Chakraborty A. Witt D. Lagona J. Damkaci F. Ofori MA. Chiles JK. Fettinger JC. Isaacs L. J. Org. Chem.  2002,  67:  5817 
8

Compound 3a: 1H NMR (300 MHz, DMSO-d 6): δ = 9.37 (s, 2 H, OH) and 8.32 (s, 2 H, OH), 7.08 (s, 10 H, ArH), 6.97 (d, 2 H, ArH, J = 8.4 Hz) and 6.48 (d, 2 H, ArH, J = 8.4 Hz), 5.36 and 3.59 (d, 4 H, ArCH2N, J = 15.9 Hz), 4.50 and 3.91 (d, 8 H, ArCH2N, J = 15.9 Hz). 13C NMR (75 MHz, DMSO-d 6): δ = 159.50, 159.06 (urea C=O), 145.24, 143.71, 138.47, 134.90, 134.33, 128.64, 128.53, 128.35, 128.17, 125.18, 113.30, 85.25, 78.73, 45.76, 45.34, 44.94, 37.05. ESI-MS (FAB): m/z = 563 [M + H]+; mp >294 °C. Compound 3b: 1H NMR (CDCl3): δ = 7.08 (s, 10 H, ArH), 6.69 (d, 2 H, ArH, J = 8.4 Hz) and 6.63 (d, 2 H, ArH, J = 8.4 Hz), 5.54 and 3.80 (d, 4 H, ArCH2N, J = 15.9 Hz), 4.72 and 4.09 (d, 4 H, ArCH2N, J = 15.9 Hz), 3.91 (s, 6 H, OCH3) and 3.78 (s, 6 H, OCH3). 13C NMR (75 MHz, CDCl3): δ = 157.70, 157.27 (urea C=O), 151.98, 146.58, 133.80, 131.14, 130.09, 128.73, 128.32, 128.25, 124.98, 110.55, 85.63, 62.50, 61.56, 60.79, 56.31, 56.07, 46.00, 45.78, 38.10. ESI-MS (FAB): m/z = 619 [M + H]+; mp >294 °C. Compound 3c: 1H NMR (CDCl3):
δ = 7.08 (s, 10 H, ArH), 6.91 (d, 2 H, ArH, J = 8.4 Hz) and 6.59 (d, 2 H, ArH, J = 8.4 Hz), 5.59 and 3.76 (d, 4 H, ArCH2N, J = 15.9 Hz), 4.70 and 4.08 (d, 4 H, ArCH2N, J = 15.9 Hz), 4.13 (q, 4 H, OCH2C, J = 10.9 Hz), 3.96 (q, 4 H, OCH2C, J = 10.9 Hz), 1.47-1.37 (br, 12 H, OCCH3). 13C NMR (75 MHz, CDCl3): δ = 158.07, 157.68 (urea C=O), 151.67, 146.49, 134.17, 131.31, 130.19, 128.78, 128.71, 128.51, 128.41, 124.79, 111.68, 85.48, 69.45, 64.17, 45.50, 37.83, 16.06, 15.22. ESI-MS (FAB): m/z = 675 [M + H]+; mp 227.4-228.1 °C.