Two Propanediurea-based Cucurbituril Analogues: Bis-ns-TD[8] and NH-ns-TD[4]

Chunhua Dai; Yenan Shen; Qiaochun Wang

doi:10.1055/s-0037-1610632

Synlett, Table of Contents

Synlett 2018; 29(18): 2381-2384
DOI: 10.1055/s-0037-1610632

letter

Two Propanediurea-based Cucurbituril Analogues: Bis-ns-TD[8] and NH-ns-TD[4]

Authors

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

Abstract

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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

cucurbiturils - propanediurea - macrocycles - condensation - supramolecular chemistry

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References

References and Notes

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13 Bis-ns-TD[8]·4NaCl TD (10 g, 64.1mmol), paraformaldehyde (5.00 g, 166.6 mmol), CaCl₂ (1 g, 9.0 mmol) and 9 M HCl (20 mL) were mixed and the solution was heated at 100 °C for 3.5 h. The resulting mixture was cooled to r.t. and the resulting precipitate was collected by filtration and washed with H₂O (150 mL). 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.
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