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Synlett 2007(16): 2533-2536  
DOI: 10.1055/s-2007-986671
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Spectral Properties of Novel Fluorescent Diethoxycarbonyl Glycoluril Derivatives

Nengfang She, Meng Gao, Liping Cao, Guodong Yin, Anxin Wu*
Key Laboratory of Pesticide and 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 19 June 2007
Publication Date:
12 September 2007 (online)

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Abstract

A novel class of fluorescent diethoxycarbonyl glycoluril derivatives with aryl alkyne side chains was synthesized via alkylation and subsequent Sonogashira cross-coupling reactions. The ­fluorescence spectra showed that these compounds exhibited good blue fluorescence with the maximum wavelengths ranging from 368 nm to 403 nm.

Key words

diethoxycarbonyl glycoluril - aryl alkyne - Sonogashira cross-coupling - fluorescence

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General Procedure for the Synthesis of Compounds 5: To a solution of Pd(PPh3)2Cl2 (36 mg, 0.05 mmol), CuI (19 mg, 0.10 mmol) and compound 4 (273 mg, 0.50 mmol) in freshly distilled Et3N (15 mL) and DMF (25 mL) under Ar atmosphere at r.t., were added phenylethynylene (204 mg, 2 mmol). The mixture was warmed to 100 °C for 14 h (monitored by TLC), and then the solvent was removed under reduced pressure. The solid residue was purified by flash chromatography (SiO2, CH2Cl2-MeOH, 50:1) to give 5a (221 mg, 0.375 mmol, 75%) as a white solid. Compound 5a: IR (KBr): 3405 (w), 3213 (w), 3066 (w), 2981 (w), 1758 (s), 1724 (s), 1709 (s), 1468 (m), 1282 (s), 1091 (m), 1032 (m), 758 (s), 689 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.34-7.56 (m, 12 H), 5.99 (s, 2 H), 4.85 (d, J = 16.0 Hz, 2 H), 4.43 (d, J = 16.0 Hz, 2 H), 4.33 (q, J = 6.8 Hz, 2 H), 4.26 (q, J = 6.8 Hz, 2 H), 1.34 (t, J = 6.8 Hz, 3 H), 1.31 (t, J = 6.8 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 165.77, 165.46, 156.89, 135.97, 132.75, 131.70, 128.55, 128.36, 125.66, 123.00, 94.95, 87.53, 82.88, 73.47, 63.72, 63.40, 44.29, 13.98, 13.82. ESI-MS: m/z = 588.9 [M + H]+, 611.0 [M + Na]+. Compound 5b: IR (KBr): 3418 (w), 3059 (w), 2981 (w), 2822 (w), 1759 (s), 1733 (s), 1702 (s), 1466 (s), 1426 (m), 1274 (m), 1136 (w), 804 (w), 774 (s) cm-1. 1H NMR (400 MHz, DMSO-d 6): δ = 8.61 (s, 2 H), 8.40 (d, J = 8.4 Hz, 2 H), 8.05 (d, J = 8.4 Hz, 2 H), 7.99 (d, J = 8.4 Hz, 2 H), 7.88 (d, J = 7.2 Hz, 2 H), 7.81 (s, 2 H), 7.57 (q, J = 8.0 Hz, 2 H), 7.50 (d, J = 7.2 Hz, 2 H), 7.12 (q, J = 8.0 Hz, 2 H), 4.79 (d, J = 16.0 Hz, 2 H), 4.58 (d, J = 16.0 Hz, 2 H), 4.28 (q, J = 7.2 Hz, 2 H), 4.17 (q, J = 7.2 Hz, 2 H), 1.28 (t, J = 7.2 Hz, 3 H), 1.23 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, DMSO-d 6): δ = 166.45, 166.00, 157.10, 138.50, 132.89, 132.82, 132.43, 131.01, 129.66, 128.53, 127.19, 126.77, 125.65, 125.52, 123.73, 119.39, 92.46, 91.85, 82.37, 74.19, 62.96, 62.72, 43.37, 13.84, 13.78. ESI-MS: m/z = 689.1 [M + H]+, 711.1 [M + Na]+. Compound 5c: IR (KBr): 3363 (s), 3261 (s), 3039 (w), 2984 (w), 2209 (w), 1769 (s), 1710 (s), 1691 (s), 1605 (s), 1514 (s), 1481 (s), 1267 (s), 1226 (m), 1144 (w), 1038 (w), 838 (w), 754 (w) cm-1. 1H NMR (400 MHz, DMSO-d 6): δ = 10.01 (s, 2 H), 8.55 (s, 2 H), 7.49 (s, 2 H), 7.39 (d, J = 8.4 Hz, 4 H), 6.82 (d, J = 8.4 Hz, 4 H), 4.65 (d, J = 16.0 Hz, 2 H), 4.48 (d, J = 16.0 Hz, 2 H), 4.25 (q, J = 7.2 Hz, 2 H), 4.15 (q, J = 7.2 Hz, 2 H), 1.25 (t, J = 7.2 Hz, 3 H), 1.21 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, DMSO-d 6): δ = 158.41, 157.03, 137.44, 133.09, 132.09, 123.89, 120.56, 115.93, 112.25, 94.54, 85.89, 82.28, 74.10, 62.88, 43.30, 13.75. ESI-MS: m/z = 621.2 [M + H]+, 643.2 [M + Na]+. Compound 5d: IR (KBr): 3347 (w), 3219 (w), 2981 (w), 2937 (w), 2207 (w), 1760 (s), 1742 (s), 1710 (s), 1604 (m), 1513 (s), 1467 (m), 1289 (m), 1247 (s), 1140 (m), 1028 (s), 832 (m), 753 (w) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.43 (s, 2 H), 7.41 (d, J = 8.8 Hz, 4 H), 6.81 (d, J = 8.8 Hz, 4 H), 6.14 (s, 2 H), 4.75 (d, J = 16.0 Hz, 2 H), 4.33 (d, J = 16.0 Hz, 2 H), 4.24 (q, J = 7.2 Hz, 2 H), 4.18 (q, J = 7.2 Hz, 2 H), 3.76 (s, 6 H), 1.26 (t, J = 7.2 Hz, 3 H), 1.22 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 165.84, 159.82, 156.96, 135.58, 133.16, 132.54, 125.73, 115.24, 114.04, 94.46, 86.55, 76.25, 63.71, 55.31, 44.32, 13.99. ESI-MS: m/z = 649.2 [M + H]+, 671.3 [M + Na]+. Compound 5e: IR (KBr): 3375 (w), 3061 (w), 2849 (w), 1754 (s), 1731 (s), 1702 (s), 1595 (s), 1458 (s), 1284 (m), 1136 (w), 1032 (w), 821 (w), 767 (w) cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.62 (d, J = 4.8 Hz, 4 H), 7.61 (s, 2 H), 7.37 (d, J = 4.8 Hz, 4 H), 6.08 (s, 2 H), 4.87 (d, J = 16.0 Hz, 2 H), 4.46 (d, J = 16.0 Hz, 2 H), 4.34 (q, J = 7.2 Hz, 2 H), 4.27 (q, J = 7.2 Hz, 2 H), 1.35 (t, J = 7.2 Hz, 3 H), 1.29 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 165.35, 156.68, 149.89, 137.24, 133.25, 130.88, 125.42, 124.90, 91.71, 91.34, 82.78, 82.45, 63.65, 44.24, 14.01. ESI-MS: m/z = 591.1 [M + H]+, 613.0 [M + Na]+. Compound 5f: IR (KBr): 3576 (w), 3203 (w), 2975 (w), 2938 (w), 2677 (m), 1759 (s), 1703 (s), 1474 (m), 1278 (m), 1033 (m), 807 (w), 768 (w) cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.77 (s, 2 H), 8.59 (s, 2 H), 7.81 (d, J = 8.0 Hz, 2 H), 7.58 (s, 2 H), 7.30 (d, J = 8.0 Hz, 2 H), 6.97 (s, 2 H), 4.85 (d, J = 16.0 Hz, 2 H), 4.43 (d, J = 16.0 Hz, 2 H), 4.32 (q, J = 7.2 Hz, 2 H), 4.22 (q, J = 7.2 Hz, 2 H), 1.33 (t, J = 7.2 Hz, 3 H), 1.26 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 165.82, 165.50, 157.05, 152.00, 148.83, 138.49, 136.84, 132.96, 124.94, 90.98, 90.47, 82.74, 73.67, 63.64, 63.42, 44.18, 13.99, 13.81. ESI-MS: m/z = 591.1 [M + H]+, 613.0 [M + Na]+. Compound 5g: IR (KBr): 3355 (s), 3200 (s), 2984 (w), 1753 (s), 1703 (s), 1711 (s), 1665 (s), 1609 (s), 1466 (m), 1408 (m), 1391 (m), 1279 (m), 1031 (w), 856 (w), 773 (w) cm-1. 1H NMR (400 MHz, DMSO-d 6): δ = 8.60 (s, 2 H), 8.09 (s, 2 H), 7.94 (d, J = 8.0 Hz, 4 H), 7.67 (d, J = 8.0 Hz, 4 H), 7.65 (s, 2 H), 7.51 (s, 2 H), 4.71 (d, J = 16.0 Hz, 2 H), 4.53 (d, J = 16.0 Hz, 2 H), 4.26 (q, J = 7.2 Hz, 2 H), 4.15 (q, J = 7.2 Hz, 2 H), 1.26 (t, J = 7.2 Hz, 3 H), 1.21 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, DMSO-d 6): δ =167.02, 166.39, 165.94, 157.01, 138.62, 134.49, 132.62, 131.24, 128.01, 124.61, 123.48, 93.43, 89.14, 82.24, 74.12, 62.90, 62.67, 43.28, 13.75. ESI-MS: m/z = 675.2 [M + H]+, 697.2 [M + Na]+. Compound 5h: IR (KBr): 3321 (m), 3103 (w), 3042 (w), 2983 (w), 2210 (w), 1707 (s), 1594 (m), 1525 (s), 1465 (m), 1404 (w), 1371 (w), 1313 (s), 1257 (m), 1033 (w), 836 (w), 764 (w) cm-1. 1H NMR (400 MHz, DMSO-d 6): δ = 10.18 (s, 2 H), 8.56 (s, 2 H), 7.66 (d, J = 8.4 Hz, 4 H), 7.53 (d, J = 8.4 Hz, 4 H), 7.50 (s, 2 H), 4.68 (d, J = 16.0 Hz, 2 H), 4.49 (d, J = 16.0 Hz, 2 H), 4.25 (q, J = 7.2 Hz, 2 H), 4.15 (q, J = 7.2 Hz, 2 H), 2.07 (s, 6 H), 1.25 (t, J = 7.2 Hz, 3 H), 1.21 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, DMSO-d 6): δ = 168.62, 165.91, 156.97, 140.05, 137.77, 132.21, 132.06, 123.76, 118.92, 116.07, 94.15, 86.79, 82.27, 74.07, 62.84, 62.61, 43.28, 24.06, 13.75. ESI-MS: m/z = 703.2 [M + H]+, 725.2 [M + Na]+.

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Crystal Data for Compound 5a: C35H32N4O7, MW = 620.65, triclinic, a = 10.133(12), b = 11.903(13), c = 14.938(17) Å, α = 68.396(2)°, β = 77.801(2)°, γ = 67.511(2)°, V = 1543(3) Å3, T = 292(2) K, space group P1, Z = 2, µ(Mo-Kα) = 0.094 mm-1, 5369 reflections measured, 2915 unique (Rint = 0.1322) which were used in all calculations. The final wR2 (F2) was 0.1957 (all data). CCDC-650493 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data Center, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 (1223)336033; email: deposit@ccdc.cam.ac.uk.