Synlett, Table of Contents Synlett 2018; 29(18): 2381-2384DOI: 10.1055/s-0037-1610632 letter © Georg Thieme Verlag Stuttgart · New York Two Propanediurea-based Cucurbituril Analogues: Bis-ns-TD[8] and NH-ns-TD[4] Chunhua Dai , Yenan Shen , Qiaochun Wang * Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. of China Email: qcwang@ecust.edu.cn › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract Two new cucurbituril members, one containing two equivalent cavities and the other having an active secondary amine group, were synthesized by condensation of propanediurea (2,4,6,8-tetraazabicyclo[3.3.1]nonane-3,7-dione) with formaldehyde. These two macrocycles exhibit excellent thermal stability, and their structures were confirmed by single-crystal X-ray diffraction, 1H NMR spectroscopy, and high-resolution mass spectrometry. Key words Key wordscucurbiturils - propanediurea - macrocycles - condensation - supramolecular chemistry Full Text References References and Notes 1a Geras’ko OA. Samsonenko DG. Fedin VP. Russ. Chem. Rev. 2002; 71: 741 1b Lee JW. Samal S. Selvapalam N. Kim H.-J. Kim K. Acc. Chem. Res. 2003; 36: 621 1c Lagona J. Mukhopadhyay P. Chakrabarti S. Isaacs L. Angew. Chem. Int. Ed. 2005; 44: 4844 1d Reany O. Li A. Yefet M. Gilson MK. Keinan E. J. Am. Chem. Soc. 2017; 139: 8138 2a Day AI. Blanch RJ. Arnold AP. Lorenzo S. Lewis GR. Dance I. Angew. Chem. Int. Ed. 2002; 41: 275 2b Khashab NM. Trabolsi A. Lau YA. Ambrogio MW. Friedman DC. Khatib HA. Zink JI. Stoddart JF. Eur. J. Org. Chem. 2009; 1669 2c Dong S. Zheng B. Wang F. Huang F. Acc. Chem. Res. 2014; 47: 1982 2d Liu Y. Yang H. Wang Z. Zhang X. Chem. 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The residual solid precipitate was collected and crystallized from 25% aq NaCl then dried to give a white solid; yield: 1.9 g (13.5%); mp >350 °C. 1H NMR (400 MHz, D2O): δ = 6.54 (d, J = 14.8 Hz, 2 H), 6.36 (dd, J = 26.3, 14.7 Hz, 12 H), 5.47 (s, 4 H), 5.20 (s, 20 H), 4.06–4.18 (m, 14 H), 2.30 (s, 8 H), 2.23 (d, J = 12.7 Hz, 4 H), 2.13 (d, J = 13.1 Hz, 4 H). 13C NMR (100 MHz, D2O, 298 K): δ = 153.46, 153.01, 152.91, 151.96, 77.67, 69.65, 69.60, 69.51, 69.42, 69.39, 66.45, 61.29, 60.87, 27.92, 27.60. MALDI-TOF MS: m/z [M + Na]+ calcd for C58H68N32NaO18: 1523.5281; found: 1523.4833. Anal. Calcd for C58H68N32O18·4NaCl (1732.3734): C, 40.18; H, 3.956; N, 25.87. Found: C, 40.12; H, 3.951; N, 25.81. 14 CCDC 1811515 and 1811514 contain the supplementary crystallographic data for bis-ns-TD[8]·4NaCl and NH-ns-TD[4]·2CaCl2 , respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures. 15 NH-ns-TD[4]·2CaCl2 The reaction filtrate from the preparation of Bis-ns-TD[8]·4NaCl (ref. 14) was concentrated to a quarter of its volume, and a yellow solid was obtained after adding acetone (5 mL) and H2O (10 mL). The solid was crystallized from H2O affording a pure white solid yield: 1.6 g; mp >350 °C. 1H NMR (400 MHz, D2O): δ = 6.50 (d, J = 15.1 Hz, 1 H), 6.29 (d, J = 15.1 Hz, 1 H), 6.19 (d, J = 15.0 Hz, 4 H), 5.44–5.16 (m, 6 H), 4.85 (s, 2 H), 4.42 (s, 2 H), 4.32–4.10 (m, 6 H), 3.85 (d, J = 10.6 Hz, 2 H), 2.31 (d, J = 26.3 Hz, 8 H). 13C NMR (100 MHz, D2O, 298K): δ = 155.71, 154.70, 154.22, 153.22, 69.75, 69.35, 68.91, 62.80, 61.74, 61.22, 60.77, 59.28, 26.89, 25.95. MALDI-TOF MS: m/z [M + Na]+ calcd for C28H35N17NaO8: 760.2747; found: 760.2252; [M + K]+ calcd for C28H35KN17O8: 776.2486; found: 776.2520. Anal. Calcd for C28H35N17O8·2CaCl2 (957.0860): C, 35.11; H, 3.685; N, 24.87. Found: C, 34.97; H, 3.659; N, 24.82. 16 Vinciguerra B. Cao L. Cannon JR. Zavalij PY. Fenselau C. Isaacs L. J. Am. Chem. Soc. 2014; 134: 131 17a Jansen RJ. Dissertation. Radboud University Nijmegen; The Netherlands: 2002 17b Ustrnul L. Kulhanek P. Lizal T. Sindelar V. Org. Lett. 2015; 17: 1022 18 Day AI. Blanch RJ. Coe A. Arnold AP. J. Inclusion Phenom. Macrocyclic Chem. 2002; 43: 247 Supplementary Material Supplementary Material Supporting Information Primary Data Primary Data
