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Synlett 2004(2): 0255-0258  
DOI: 10.1055/s-2003-44981
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Novel Cascade Reaction of Aryl Aldoxime with Dimedone Under Microwave Irradiation: The Synthesis of N-Hydroxylacridine

Shujiang Tu*a, Chunbao Miaoa, Yuan Gaob, Fang Fanga, Qiya Zhuanga, Youjian Fenga, Daqing Shia
a Department of Chemistry, Xuzhou Normal University, Key Laboratory of Biotechnology on Medical Plant, Xuzhou; Jiangsu, 221009, P. R. China
Fax: +86(516)3403164; e-Mail: laotu2001@263.net;
b Department of Chemistry, Shenzhen University, Shenzhen; Guangdong, 518060, P. R. China
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Publication History

Received 28 August 2003
Publication Date:
08 December 2003 (online)

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Abstract

A novel sequential addition, elimination and cyclization reactions took place when aldoxime and dimedone in glycol was subjected to microwave irradiation and a new type of N-hydroxyl­acridinedione derivatives was obtained in excellent yields (80-95%) within a short reaction time (4-8 min).

Key words

aryl aldoxime - dimedone - N-hydroxylacridine - microwave

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The General Procedure is Represented Below: The mixture of substituted aryl aldeoxime (2 mmol) and dimedone (4 mmol) in glycol (5 mL) was irradiated for 4-6 min. The reaction mixture was cooled to r.t. and poured into 50 mL of H2O, filtered to give the crude product, which was further purified by recrystallization from 95% EtOH. All products are characterized by IR and 1H NMR spectral data. Typical spectral data: compound 3i: IR (KBr): 3285, 3069, 2957, 2867, 1624, 1605, 1483, 1396, 1364, 1251, 1170, 1141, 1069, 1012, 981, 922, 886, 816, 773, 728, 599, 567 cm-1. 1H NMR (DMSO-d 6): d = 0.92 (s, 6 H, 2 × CH3), 1.02 (s, 6 H, 2 × CH3), 2.03-2.41 (m, 8 H, 4 × CH2), 4.98 (s, 1 H, CH), 5.81 (d, 1 H, J = 3.00 Hz, furan H), 6.21 (dd, 1 H, J = 3.08 Hz, furan H), 7.35 (d, 1 H, J = 0.90 Hz, furan H), 9.36 (s, 1 H, NH). Compound 3j: IR (KBr): 3280, 3209, 3068, 2959, 2930, 2871, 2721, 1645, 1600, 1488, 1381, 1309, 1273, 1244, 1225, 1188, 1169, 1143, 1121, 1065, 1006, 885, 870, 775, 733, 693, 648, 618, 572, 560 cm-1. 1H NMR (DMSO-d 6): d = 0.63 (t, 3 H, J = 7.56 Hz, CH3), 1.02 (s, 12 H, 4 Ž CH3), 1.24-1.26 (m, 2 H, CH2), 2.02-2.27 (m, 8 H, 4 × CH2), 3.80 (t, 1 H, J = 5.25 Hz, CH), 8.99 (s, 1 H, NH). Compound 4c: IR (KBr): 3300, 2961, 2878, 2674, 1603, 1568, 1490, 1409, 1371, 1323, 1272, 1225, 1141, 1023, 902, 848, 565, 523 cm-1. 1H NMR (DMSO-d 6): d = 0.87 (s, 6 H, 2 × CH3), 1.04 (s, 6 H, 2 × CH3), 2.02-2.68 (m, 8 H, 4 × CH2), 4.93 (s, 1 H, CH), 7.14 (d, 2 H, J = 6.3 Hz, Ar H), 7.25 (d, 2 H, J = 6.3 Hz, Ar H), 10.79 (s, 1 H, OH). Compound 4i: IR (KBr): 3225, 2954, 2871, 1667, 1660, 1504, 1462, 1504, 1462, 1369, 1229, 1154, 1010, 808, 661, 582 cm-1. 1H NMR (DMSO-d 6): d = 0.82 (s, 12 H, 4 Ž CH3), 1.02 (s, 12 H, 4 Ž CH3), 2.00-2.65 (m, 16 H, 8 Ž CH2), 4.47 (s, 2 H, 2 Ž CH), 6.95 (s, 4 H, Ar H), 10.73 (s, 2 H, 2 Ž OH). Compound 4j: IR (KBr): 3308, 2958, 2930, 2867, 2728, 1605, 1562, 1501, 1469, 1359, 1324, 1262, 1220, 1142, 1072, 1007, 1072, 979, 951, 921, 884, 781, 727, 683, 616, 600, 566 cm-1. 1H NMR (DMSO-d 6): d = 0.94 (s, 6 H, 2 × CH3), 1.05 (s, 6 H, 2 × CH3), 2.07-2.61 (m, 8 H, 4 × CH2), 5.12 (s, 1 H, CH), 5.84 (d, 1 H, J = 3.3 Hz, furan H), 6.25 (dd, 1 H, J = 3.0 Hz, furan H), 7.35 (d, 1 H, J = 0.81 Hz, furan H), 10.85 (s, 1 H, OH). Compound 4k: IR (KBr): 3278, 3186, 3052, 2945, 1644, 1603, 1490, 1362, 1229, 1173, 1127, 1034 cm-1. 1H NMR (DMSO-d 6): d = 1.76-1.95 (m, 4 H, CH2), 2.19-2.22 (m, 4 H, =C-CH2-), 2.29-2.48 (m, 4 H, -CO-CH2-), 3.67 (s, 3 H, CH3), 4.85 (s, 1 H, CH), 6.72 (d, 2 H, J = 8.4Hz, Ar H), 7.05 (d, 2 H, J = 8.4 Hz, Ar H), 9.37 (s, 1 H, OH). Compound 4n: IR (KBr): 3298, 2962, 2958, 2966, 2657, 1627, 1552, 1464, 1389, 1298, 1233, 1172, 1144, 1074, 1002, 934, 905, 887, 778, 740, 685, 612,3, 567 cm-1. 1H NMR (DMSO-d 6): d = 0.66 (t, 3 H, J = 7.50 Hz, CH3,), 1.02 (s, 6 H, 2 Ž CH3), 1.05 (s, 6 H, 2 Ž CH3), 1.16-1.20 (m, 2 H, CH2), 2.06-2.63 (m, 8 H, 4 × CH2), 3.85 (t, 1 H, J = 5.25 Hz, CH), 10.60 (s, 1 H, OH).

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The sing-crystal growth was carried out in EtOH at r.t. X-ray crystallographic analysis was performed with a Siemens SMART CCD and a Siemens P4 diffractometer (graphite monochromator, MoKα radiation λ = 0.71073 Å). The crystal crystallizes with one water molecule. Crystal data for 3g: C24H29NO3, yellow, crystal dimension 0.80 × 0.80 × 0.30 mm, orthorhombic, space group Pca2 (1), a = 1.41862 (3), b = 1.51896 (3), c = 2.07611 (1) Å, α = γ = β = 90°, V = 4.47366(13) Å3, M r = 379.48, Z = 8, D c = 1.27 g/cm3, λ = 0.071073 Å, µ (MoKα) = 0.074 mm-1, F(000) = 1632, S = 1.144, R 1 = 0.0652, wR 2 = 0.1510. Crystal data for 4a: C23H28ClFNO4, yellow, crystal dimension 0.58 × 0.58 × 0.40 mm, monoclinic, space group P2(1)/c, a = 12.638(2), b = 14.039 (3), c = 11.102 (2) Å, = 94.60 (1)°, V = 2140.2 (6) Å3, M r = 401.46, Z = 4, Dc = 1.246 g/cm3, λ = 0.71073 Å, µ (MoKα) = 0.09 mm-1, F(000) = 856, S = 0.906, R 1 = 0.0398, wR 2 = 0.0932.