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DOI: 10.1055/s-2004-820022
Clean Synthesis of 1,8-Dioxo-octahydroxanthene Derivatives Catalyzed by p-Dodecylbenezenesulfonic Acid in Aqueous Media
Publication History
Publication Date:
04 March 2004 (online)
Abstract
An efficient and convenient approach to the synthesis of 3,3,6,6-tetramethyl-9-aryl-1,8-dioxo-octahydroxanthene derivatives using p-dodecylbenezenesulfonic acid (DBSA) as the catalyst (10 mol%) is described. This method provides several advantages such as being environmentally friendly, processing high yields and simple work-up procedure. In addition, water was chosen as a green solvent.
Key words
octahydroxanthene - p-dodecylbenezenesulfonic acid - clean synthesis - aqueous media
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References
General Procedure for the Preparation of 1,8-Dioxo-octahydroxanthene: A mixture of an aromatic aldehyde (1.0 mmol), 5,5-dimethyl-1,3-cyclohexanedione (2.0 mmol) and DBSA (10 mol%) in H2O (20 mL) was stirred at refluxing for 6 h. The progress of the reaction was monitored by thin layer chromatograph. After completion of the reactions, the mixture was cooled to r.t. and solid was filtered off and washed with H2O (40 mL) and the crude products isolated. The crude products were purified by recrystallization by EtOH (95%). Data of the compounds are shown below:
Compound 3a, 3,3,6,6-Tetramethyl-9-benzene-1, 8-dioxo-octahydroxanthene. Mp 202-204 °C (from EtOH). IR (KBr): νmax = 3030, 2980, 1685, 1670, 1470, 1360, 1200, 1170, 1140, 1005, 740, 700 cm-1. 1H NMR (CDCl3): δ = 098 (s, 6 H, 2 × CH3), 1.12 (s, 6 H, 2 × CH3), 2.20 (dd, 4 H, J = 1.6 Hz, J = 2.4 Hz, 2 × CH2, H-4, H-5), 2.45 (s, 4 H, 2 × CH2, H-2, H-7), 4.66 (s, 1 H, H-9), 7.21 (m, 5 H, Ar-H). Anal. Calcd for C23H26O3: C, 78.83; H, 7.47. Found: C, 78.95; H, 7.42.
Compound 3b, 3,3,6,6-Tetramethyl-9-(4-chlorophenyl)-1,8-dioxo-octahydroxanthene. Mp 228-230 °C (from EtOH). IR (KBr): νmax = 3025, 2980, 1680, 1660, 1620, 1490, 1480, 1360, 1200, 1170, 1140, 1090, 1010, 1000, 850, 840 cm-1. 1H NMR (CDCl3): δ = 0.98 (s, 6 H, 2 × CH3), 1.10 (s, 6 H, 2 × CH3), 2.23 (dd, 4 H, J = 1.6 Hz, J = 3.6 Hz, 2 × CH2, H-4, H-5), 2.50 (s, 4 H, 2 × CH2, H-2, H-7), 4.64 (s, 1 H, H-9), 7.26-7.43 (m, 4 H, ArH). Anal. Calcd for C23H25ClO3: C, 71.77; H, 6.54. Found: C, 71.89; H, 6.45.
Compound 3c, 3,3,6,6-Tetramethyl-9-(3-chlorophenyl)-1,8-dioxo-octahydroxanthene. Mp 183-184 °C (from EtOH). IR (KBr): νmax = 3030, 2980, 1685, 1660, 1620, 1490, 1475, 1365, 1200, 1170, 1135, 1095, 1000, 850, 840 cm-1. 1H NMR (CDCl3): δ = 1.02 (s, 6 H, 2 × CH3), 1.12 (s, 6 H, 2 × CH3), 2.30 (dd, 4 H, J = 1.6 Hz, J = 3.6 Hz, 2 × CH2, H-4, H-5), 2.49 (s, 4 H, 4 × CH2, H-2, H-7), 4.74 (s, 1 H, H-9), 7.11-7.25 (m, 4 H, ArH). Anal. Calcd for C23H25ClO3: C, 71.77; H, 6.54. Found: C, 71.92; H, 6.41.
Compound 3d, 3,3,6,6-Tetramethyl-9-(2-chlorophenyl)-1,8-dioxo-octahydroxanthene. Mp 228-230 °C (from EtOH). IR (KBr): νmax = 3030, 2980, 1680, 1665, 1620, 1495, 1470, 1360, 1200, 1170, 1140, 1100, 1000, 850, 840 cm-1. 1H NMR (CDCl3): δ = 0.98 (s, 6 H, 2 × CH3), 1.10 (s, 6 H, 2 × CH3), 2.06 (dd, 4 H, J = 1.6 Hz, J = 3.0 Hz, 2 × CH2, H-4, H-5), 2.49 (s, 4 H, 2 × CH2, H-2, H-7), 4.64 (s, 1 H, H-9), 7.26-7.35 (m, 4 H, ArH). Anal. Calcd for C23H25ClO3: C, 71.77; H, 6.54. Found: C, 71.88; H, 6.35.
Compound 3e, 3,3,6,6-Tetramethyl-9-(2,4-dichlorophenyl)-1,8-dioxo-octahydroxanthene. Mp 253-254 °C (from EtOH). IR (KBr): νmax = 3035, 2980, 1685, 1660, 1633, 1490, 1480, 1410, 1360, 1210, 1195, 1155, 1100, 1000, 850, 770 cm-1. 1H NMR (CDCl3): δ = 1.03 (s, 6 H, 2 × CH3), 1.12 (s, 6 H, 2 × CH3), 2.21 (dd, 4 H, J = 1.6 Hz, J = 3.2 Hz, 2 × CH2, H-4, H-5), 2.46 (s, 4 H, 2 × CH2, H-2, H-7), 4.96 (s, 1 H, H-9), 7.18 (s, 1 H, ArH), 7.39 (d, 2 H, J = 8.4 Hz, ArH). Anal. Calcd for C23H24Cl2O3: C, 65.87; H, 5.73. Found: C, 65.96; H, 5.59.
Compound 3f, 3,3,6,6-Tetramethyl-9-(2-nitrophenyl)-1,8-dioxo-octahydroxanthene. Mp 247-249 °C (from EtOH). IR (KBr): νmax = 3035, 2980, 1685, 1673, 1620, 1533, 1360, 1211, 1173, 1152, 1010, 860, 800, 780, 745, 703 cm-1. 1H NMR (CDCl3): δ = 0.99 (s, 6 H, 2 × CH3), 1.12 (s, 6 H, 2 × CH3), 2.16 (dd, 4 H, J = 1.6 Hz, J = 3.6 Hz, 2 × CH2, H-4, H-5), 2.41 (s, 4 H, 2 × CH2, H-2, H-7), 5.61 (s, 1 H, H-9), 7.36-7.45 (m, 4 H, ArH). Anal. Calcd for C23H25NO5: C, 69.85; H, 6.37; N, 3.54. Found: C, 69.93; H, 6.54; N, 3.36.
Compound 3g, 3,3,6,6-Tetramethyl-9-(3-nitrophenyl)-1,8-dioxo-octahydroxanthene. Mp 168-170 °C (from EtOH). IR (KBr): νmax = 3030, 2980, 1680, 1675, 1625, 1535, 1365, 1335, 1210, 11750, 1145, 1006, 830, 765, 730, 700 cm-1. 1H NMR (CDCl3): δ = 1.02 (s, 6 H, 2 × CH3), 1.13 (s, 6 H, 2 × CH3), 2.22 (dd, 4 H, J = 1.6 Hz, J = 3.6 Hz, 2 × CH2, H-4, H-5), 2.53 (s, 4 H, 2 × CH2, H-2, H-7), 4.85 (s, 1 H, H-9), 7.43 (s, 1 H, ArH), 7.88-7.95 (m, 3 H, ArH). Anal. Calcd for C23H25NO5: C, 69.85; H, 6.37; N, 3.54. Found: C, 69.90; H, 6.50; N, 3.42.
Compound 3h, 3,3,6,6-Tetramethyl-9-(4-nitrophenyl)-1,8-dioxo-octahydroxanthene. Mp 226-228 °C (from EtOH). IR (KBr): νmax = 3030, 2980, 1665, 1650, 1623, 1530, 1360, 1340, 1200, 1070, 1042, 1005, 875, 833 cm-1. 1H NMR (CDCl3): δ = 1.00 (s, 6 H, 2 × CH3), 1.12 (s, 6 H, 2 × CH3), 2.16 (dd, 4 H, J = 1.6 Hz, J = 3.6 Hz, 2 × CH2, H-4, H-5), 2.41 (s, 4 H, 2 × CH2, H-2, H-7), 4.46 (s, 1 H, H-9), 7.50-7.63 (m, 2 H, ArH), 8.06-8.16 (m, 2 H, ArH). Anal. Calcd for C23H25NO5: C, 69.85; H, 6.37; N, 3.54. Found: C, 69.89; H, 6.46; N, 3.40.
Compound 3i, 3,3,6,6-Tetramethyl-9-(4-hydroxy-phenyl)-1,8-dioxo-octahydroxanthene. Mp 246-248 °C (from EtOH). IR (KBr): νmax = 3360, 3025, 2980, 1795, 1725, 1700, 1633, 1613, 1525, 1390, 1375, 1260, 1233, 1200, 1196, 850, 843 cm-1. 1H NMR (CDCl3): δ = 0.99 (s, 6 H, 2 × CH3), 1.10 (s, 6 H, 2 × CH3), 2.13 (dd, 4 H, J = 1.6 Hz, J = 4.0 Hz, 2 × CH2, H-4, H-5), 2.47 (s, 4 H, 2 × CH2, H-2, H-7), 4.62 (s, 1 H, H-9), 6.77 (d, 2 H, J = 8.0 Hz, ArH), 6.98 (d, 2 H, J = 8.0, ArH). Anal. Calcd for C23H26O4: C, 75.38; H, 7.15. Found: C, 75.26; H, 7.09.
Compound 3j, 3,3,6,6-Tetramethyl-9-(4-methoxy-phenyl)-1,8-dioxo-octahydroxanthene. Mp 242-244 °C (from EtOH). IR (KBr): νmax = 3025, 2980, 1685, 1660, 1620, 1513, 1450, 1375, 1360, 1260, 1235, 1170, 1142, 1032, 1003, 840 cm-1. 1H NMR (CDCl3): δ = 1.01 (s, 6 H, 2 × CH3), 1.09 (s, 6 H, 2 × CH3), 2.20 (dd, 4 H, J = 1.6 Hz, J = 2.0 Hz, 2 × CH2, H-4, H-5), 2.46 (s, 4 H, 2 × CH2, H-2, H-7), 3.73 (s, 3 H, CH3O), 4.70 (s, 1 H, H-9), 6.67-7.28 (m, 4 H, ArH). Anal. Calcd for C24H28O4: C, 75.76; H, 7.41. Found: C, 75.85; H, 7.31.
Compound 3k, 3,3,6,6-Tetramethyl-9-(4-dimethyl-aminophenyl)-1,8-dioxo-octahydroxanthene. Mp 226-228 °C (from EtOH). IR (KBr): νmax = 3035, 2980, 2195, 1687, 1665, 1580, 1500, 1454, 1400, 1234, 1195, 1040, 811, 743 cm-1. 1H NMR (CDCl3): δ = 1.02 (s, 6 H, 2 × CH3), 1.11 (s, 6 H, 2 × CH3), 2.21 (dd, 4 H, J = 1.6 Hz, J = 2.4 Hz, 2 × CH2, H-4, H-5), 2.46 (s, 4 H, 2 × CH2, H-2, H-7), 2.88 [s, 6 H, -N(CH3)2], 4.67 (s, 1 H, H-9), 6.62 (s, 2 H, ArH), 7.15 (s, 2 H, ArH). Anal. Calcd for C25H31NO3: C, 76.34; H, 7.89; N, 3.56. Found: C, 76.48; H, 7.86; N, 3.43.
Compound 3l, 3,3,6,6-Tetramethyl-9-(4-methylphenyl)-1,8-dioxo-octahydroxanthene. Mp 217-218 °C (from EtOH). IR (KBr): νmax = 3035, 2980, 1685, 1665, 1633, 1515, 1470, 1365, 1200, 1165, 1140, 790, 775cm-1. 1H NMR (CDCl3): δ = 1.03 (s, 6 H, 2 × CH3), 1.12 (s, 6 H, 2 × CH3), 2.07 (dd, 4 H, J = 1.6 Hz, J = 2.4 Hz, 2 × CH2, H-4, H-5), 2.40 (s, 4 H, 2 × CH2, H-2, H-7), 2.43 (s, 3 H, CH3Ar), 4.69 (s, 1 H, H-9), 6.80-7.28 (m, 4 H, ArH). Anal. Calcd for C24H28O3: C, 79.08; H, 7.74. Found: C, 79.25; H, 7.59.
Compound 3m, 3,3,6,6-Tetramethyl-9-(4-hydroxy-3-methoxyphenyl)-1,8-dioxo-octahydrox-anthene. Mp 226-228 °C (from EtOH). IR (KBr): νmax = 3443, 3030, 2985, 2195, 1687, 1660, 1580, 1500, 1454, 1400, 1234, 1195, 1040, 811, 743 cm-1. 1H NMR (CDCl3): δ = 1.02 (s, 6 H, 2 × CH3), 1.12 (s, 6 H, 2 × CH3), 2.24 (d, 4 H, J = 3.6 Hz, 2 × CH2, H-4, H-5), 2.47 (s, 4 H, 2 × CH2, H-2, H-7), 3.91 (s, 3 H, OCH3), 4.68 (s, 1 H, H-9), 5.49 (s, 1 H, OH), 6.60 (s, 1 H, ArH), 6.74 (s, 1 H, ArH), 7.03 (s, 1 H, ArH). Anal. Calcd for C24H28O5: C, 77.84; H, 7.57. Found: C, 77.98; H, 7.43.
Compound 3n, 3,3,6,6-Tetramethyl-9-(3,4-dioxy-methylenephenyl)-1,8-dioxo-octahydrox-anthene. Mp 224-226 °C (from EtOH). IR (KBr): νmax = 3030, 2980, 1725, 1680, 1560, 1510, 1495, 1445, 1383, 1360, 1320, 1275, 1230, 1045, 945, 920, 890, 812, 790 cm-1. 1H NMR (CDCl3): δ = 1.00 (s, 6 H, 2 × CH3), 1.13 (s, 6 H, 2 × CH3), 2.16 (dd, 4 H, J = 1.6 Hz, J = 2.8 Hz, 2 × CH2, H-4, H-5), 2.41 (s, 4 H, 2 × CH2, H-2, 7), 4.58 (s, 1 H, H-9), 5.90 (s, 2 H, OCH2O), 6.75-6.86 (m, 3 H, ArH). Anal. Calcd for C24H26O5: C, 73.07; H, 6.64. Found: C, 73.16; H, 6.68.
Compound 3o, 3,3,6,6-Tetramethyl-9-(2-phenylethylene)-1,8-dioxo-octahydroxanthene. Mp 175-177 °C (from EtOH). IR (KBr): νmax = 3035, 2980, 1710, 1670, 1600, 1580, 1500, 1454, 1400, 1375, 1310, 1264, 1210, 1040, 970, 740, 700 cm-1. 1H NMR (CDCl3): δ = 1.14 (s, 12 H, 4 × CH3), 2.32 (s, 4 H, 4 × CH2), 2.46 (s, 4 H, 4 × CH2), 4.42 (s, 1 H, H-9), 6.25-6.33 (m, 2 H, -CH=CH-), 7.18-7.28 (m, 5 H, ArH). Anal. Calcd for C25H28O3: C, 79.79; H, 7.45. Found: C, 79.91; H, 7.30.
Compound 8b, 2,2′-(4-Chlorophenyl)methylene-bis(3-hydroxy-5,5-dimethyl-2-cyclohexene- 1-one). Mp 141-143 °C (from EtOH), 140-142 °C(reported).10 IR (KBr): νmax = 3443, 3000˜2500, 2980, 2922, 1635, 1490, 1480, 1380, 1290, 1230, 1140, 1090, 1000, 745 cm-1. 1H NMR (CDCl3): δ = 1.06 (s, 6 H, 2 × CH3), 1.17 (s, 6 H, 2 × CH3), 2.21 (d, 4 H, J = 2.8 Hz, 2 × CH2), 2.53 (s, 4 H, 4 × CH2), 5.62 (s, 1 H, CH), 7.09-7.40 (m, 4 H, ArH), 9.63 (br, s, 1 H, OH, enol), 11.88 (br, s, 1 H, OH, enol). Anal. Calcd for C23H27ClO4: C, 68.59; H, 6.75. Found: C, 68.66; H, 6.53.