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Synlett 2009(2): 315-319  
DOI: 10.1055/s-0028-1087670
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Novel Molecular Clips via Click Chemistry Based on Diethoxy carbonyl Glycoluril

Meng Gao, Liping Cao, Zihua Wang, Jingjing Sun, Nengfang She, Anxin Wu*
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, Central China Normal University, Wuhan 430079, P. R. of China
e-Mail: chwuax@mail.ccnu.edu.cn;
Further Information

Publication History

Received 8 September 2008
Publication Date:
15 January 2009 (online)

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Abstract

A novel class of molecular clips based on diethoxycarbonyl glycoluril was synthesized via click chemistry. Seven different arylacetylenes were used in this research, and all reaction products gave satisfying ¹H NMR, ¹³C NMR, HRMS, and IR spectra. The structure and conformation of 7a were further confirmed by single-crystal X-ray diffraction. A primary study on the metal-ion binding ability of 7f showed that its fluorescence was obviously quenched by Fe³+, Ag+, and Cu²+ among metal ions examined.

Key words

clip receptor - diethoxycarbonyl glycoluril - molecular recognition - 1,2,3-triazole - fluorescence

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Compound 5: IR (KBr): 2984, 1721, 1598, 1415, 1358, 1176, 907, 817, 663, 554 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 8.4 Hz, 4 H), 7.35 (d, J = 8.4 Hz, 4 H), 4.73 (d, J = 14.4 Hz, 4 H), 4.30-4.25 (m, 8 H), 4.04 (t, J = 5.2 Hz, 4 H), 2.90 (t, J = 5.2 Hz, 4 H), 2.48 (s, 6 H), 1.30 (t, J = 7.2 Hz, 6 H). ¹³C NMR (150 MHz, CDCl3): δ = 164.8, 158.3, 144.8, 132.5, 129.7, 127.7, 75.8, 67.2, 63.3, 59.7, 49.7, 21.4, 13.6. ESI-MS: m/z = 765.0 [M + H]+.

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Compound 6: IR (KBr): 2989, 2100, 1767, 1709, 1407, 1276, 899, 725 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 4.88 (d, J = 14.0 Hz, 4 H), 4.36 (d, J = 14.0 Hz, 4 H), 4.30 (q, J = 7.2 Hz, 4 H), 3.36 (t, J = 5.6 Hz, 4 H), 2.90 (t, J = 5.6 Hz, 6 H), 1.32 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, CDCl3): δ = 165.0, 158.4, 76.0, 63.4, 59.9, 50.4, 48.6, 13.8. ESI-MS: m/z = 506.2 [M]+.

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General Procedure for the Synthesis of Compound 7
The azide 6 (0.20 mmol) and arylacetylene (0.40 mmol) were suspended in 1:1 mixture of H2O and t-BuOH (10 mL). Ascorbate acid (0.020 mmol, 20 µL of freshly prepared 1.0 M solution in H2O, 10 mol%) was added, followed by copper(II) sulfate pentahydrate (0.010 mmol, 100 µL of 0.10 M solution in H2O, 5.0 mol%). The heterogeneous mixture was stirred vigorously for 24 h under Ar protection. After total consumption of the starting material (determination by TLC), the solvent was removed in vacuo, and the residue was isolated by column chromatography on SiO2 to get the pure product 7.
Compound 7a: IR (KBr): 3244, 2985, 1705, 1444, 1282, 1047, 767, 697 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.86 (d, J = 7.6 Hz, 4 H), 7.60 (s, 2 H), 7.45 (t, J = 7.6 Hz, 4 H), 7.35 (t, J = 7.6 Hz, 2 H), 4.82 (d, J = 13.6 Hz, 4 H), 4.36 (t, J = 6.0 Hz, 4 H), 4.28 (q, J = 7.2 Hz, 4 H), 4.19 (d, J = 13.6 Hz, 4 H), 2.93 (t, J = 6.0 Hz, 4 H), 1.30 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, CDCl3): δ = 164.9, 158.6, 147.3, 130.6, 128.9, 128.1, 125.6, 120.3, 76.0, 63.5, 60.0, 50.1, 47.0, 13.8. ESI-HRMS: m/z [M + Na]+ calcd for C34H38N12NaO6: 733.2929; found: 733.2898.
Compound 7b: IR (KBr): 3423, 3137, 2988, 1766, 1730, 1707, 1612, 1411, 1286, 1234, 1045, 907, 718 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 8.68 (d, J = 5.6 Hz, 4 H), 7.88 (s, 2 H), 7.77 (d, J = 5.6 Hz, 4 H), 4.81 (d, J = 13.6 Hz, 4 H), 4.45 (t, J = 5.2 Hz, 4 H), 4.31-4.22 (m, 8 H), 3.03 (t, J = 5.2 Hz, 4 H), 1.31 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, CDCl3): δ = 164.7, 158.5, 150.3, 144.9, 137.9, 122.0, 119.8, 75.9, 63.6, 59.9, 50.1, 47.6, 13.8. ESI-HRMS: m/z [M+Na]+ calcd for C32H36N14NaO6: 735.2834; found: 735.2814.
Compound 7c: IR (KBr): 3447, 3134, 2939, 2840, 1760, 1718, 1459, 1299, 1248, 1231, 1027, 825, 717 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 8.4 Hz, 4 H), 7.50 (s, 2 H), 6.97 (d, J = 8.4 Hz, 4 H), 4.82 (d, J = 13.2 Hz, 4 H), 4.33-4.25 (m, 8 H), 4.18 (d, J = 13.2 Hz, 4 H), 3.80 (s, 6 H), 2.88 (t, J = 6.0 Hz, 4 H), 1.30 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, CDCl3): δ = 164.9, 159.5, 158.5, 147.2, 126.9, 123.3, 119.5, 114.2, 76.0, 63.5, 60.0, 55.2, 50.1, 46.8, 13.8. ESI-HRMS: m/z [M + Na]+ calcd for C36H42N12NaO8: 793.3141; found: 793.3100.
Compound 7d: IR (KBr): 3448, 3367, 2982, 2849, 1720, 1621, 1502, 1416, 1291, 1233, 1029, 906, 837, 715 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.61 (d, J = 8.0 Hz, 4 H), 7.48 (s, 2 H), 6.68 (d, J = 8.0 Hz, 4 H), 4.79 (d, J = 13.6 Hz, 4 H), 4.28-4.24 (m, 8 H), 4.12 (d, J = 13.6 Hz, 4 H), 3.90 (br s, 4 H), 2.87 (t, J = 6.0 Hz, 4 H), 1.27 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, CDCl3): δ = 164.9, 158.5, 147.6, 146.7, 126.7, 120.6, 119.1, 115.1, 76.0, 63.5, 59.9, 50.0, 46.7, 13.8. ESI-HRMS: m/z [M + Na]+ calcd for C34H40N14NaO6: 763.3147; found: 763.3120.
Compound 7e: IR (KBr): 3362, 3150, 2984, 2844, 1726, 1678, 1617, 1414, 1235, 1030, 982, 910, 858, 776, 713 cm-¹. ¹H NMR (400 MHz, DMSO-d 6): δ = 8.50 (s, 2 H), 8.02 (s, 2 H), 7.98 (d, J = 8.0 Hz, 4 H), 7.91 (d, J = 8.0 Hz, 4 H), 7.42 (s, 2 H), 4.78 (d, J = 13.6 Hz, 4 H), 4.50 (t, J = 6.0 Hz, 4 H), 4.29-4.21 (m, 8 H), 3.01 (t, J = 6.0 Hz, 4 H), 1.21 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, DMSO-d 6): δ = 167.5, 164.9, 158.3, 145.4, 133.4, 133.3, 128.3, 124.8, 122.5, 75.8, 63.5, 59.3, 49.6, 46.9, 13.7. ESI-HRMS: m/z [M + Na]+ calcd for C36H40N14NaO8: 819.3046; found: 819.2999.
Compound 7f: IR (KBr): 3423, 3137, 2988, 1766, 1730, 1707, 1612, 1411, 1286, 1234, 1045, 907, 718 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 8.43 (d, J = 8.0 Hz, 2 H), 7.82 (d, J = 8.0 Hz, 4 H), 7.70 (d, J = 8.0 Hz, 2 H), 7.55-7.47 (m, 8 H), 4.82 (d, J = 13.6 Hz, 4 H), 4.34 (t, J = 6.0 Hz, 4 H), 4.27 (q, J = 7.2 Hz, 4 H), 4.20 (d, J = 13.6 Hz, 4 H), 2.95 (t, J = 6.0 Hz, 4 H), 1.28 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, CDCl3): δ = 164.8, 158.5, 146.5, 133.7, 130.7, 128.8, 128.3, 127.8, 127.1, 126.7, 126.0, 125.4, 125.3, 122.9, 75.9, 63.5, 60.0, 50.2, 47.1, 13.8. ESI-HRMS: m/z [M + Na]+ calcd for C42H42N12NaO6: 833.3242; found: 833.3220.
Compound 7g: IR (KBr): 3448, 3122, 2982, 1719, 1414, 1232, 1035, 906, 821, 712, 505, 488 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.47 (s, 2 H), 4.81-4.78 (m, 8 H), 4.34-4.30 (m, 8 H), 4.27 (q, J = 7.2 Hz, 4 H), 4.20 (d, J = 13.2 Hz, 4 H), 4.10 (s, 10 H), 2.94 (t, J = 5.6 Hz, 4 H), 1.29 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, CDCl3): δ = 164.9, 158.5, 146.4, 119.5, 76.0, 75.5, 69.6, 68.6, 66.5, 63.5, 60.0, 50.3, 47.1, 13.8. ESI-HRMS: m/z [M + Na]+ calcd for C42H46Fe2N12NaO6: 949.2273; found:949.2215.

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Crystal Data for Compound 7a
C34H38N12O6, MW = 710.78, triclinic, a = 10.0153 (5), b = 12.0495 (6), c = 16.3995 (8) Å, α = 102.658 (0)˚, β = 103.272 (0)˚, γ = 108.398 (0)˚, V = 1734.28 (15) ų, T = 294 (2) K, space group Z = 4, m(MoKα) = 0.094 mm-¹, 15230 reflections measured, 6724 unique (Rint = 0.0981) which were used in all calculations. The final wR 2 (F 2) was 0.1531. CCDC 699457 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.