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Synlett 2003(11): 1647-1650
DOI: 10.1055/s-2003-41422
LETTER
© Georg Thieme Verlag Stuttgart · New York

An Expedient Synthesis of Unusual Oxoisoaporphine and Annelated Quinoline Derivatives

Eduardo Sobarzo-Sánchez*a, Bruce K. Casselsa, Luis Castedob
a Department of Chemistry, Faculty of Sciences, and Millennium Institute for Advanced Studies in Cell Biology and Biotechnology, University of Chile, Casilla 653, Santiago, Chile
e-Mail: esobarzo@usc.es;
b Department of Organic Chemistry and C.S.I.C. Associated Unit, Faculty of Chemistry, University of Santiago, 15782 Santiago de Compostela, Spain
Further Information

Publication History

Received 6 January 2003
Publication Date:
22 September 2003 (online)

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Abstract

Several 2,3-dihydro-7H-dibenzo[de,h]quinolin-7-ones and 7H-dibenzo[de,h]quinolin-7-ones were catalytically hydro­genated over PtO2 in acetic acid to afford 7-hydroxyquinoline and quinolone derivatives with reduced benzene rings.

Key words

7H-dibenzo[de,h]quinolin-7-ones - oxoisoaporphines - catalytic hydrogenation - reductions - chemoselectivity

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Representative Experimental Procedure: A yellow solution of 2, mp 164-165 ºC, prepared as described,4 (0.5 g, 1.90 mmol) in 50 mL of AcOH was hydrogenated at 68 psi over PtO2 (0.3 g) for 24 h at r.t. The colorless solution was diluted with 100 mL water, neutralized with NH3 and extracted with CHCl3 (200 mL). The CHCl3 extract was dried over Na2SO4 and concentrated to dryness, and the residue subjected to flash column chromatography on silica gel, eluting with 90:10 EtOAc-hexane (v/v) to give 5 (0.390 g, 77% yield), which crystallized in MeOH as yellowish needles.
Spectroscopic data of 4: 1H NMR (CDCl3, 300 MHz): δ 1.75 (m, 4 H), 2.57 (broad s, 2 H), 2.74 (broad s, 2 H), 2.85 (t, 2 H, J = 7.8 Hz), 4.11 (t, 2 H, J = 7.8 Hz), 7.37 (d, 1 H, J = 7.8 Hz), 7.47 (dd, 1 H, J = J′ = 7.7 Hz), 7.94 (d, 1 H, J = 7.8 Hz). 13C NMR (CDCl3, 75 MHz): δ 22.01, 22.09, 23.58, 24.72, 24.93, 48.85, 124.7, 125.0, 129.1, 131.3, 132.1, 135.2, 139.0, 146.7, 158.5, 185.8. IR (KBr): 2929, 2876, 2855, 1639, 1593, 1296 cm-1. Mp 149-150 ºC. Anal. Calcd. for C16H15NO: C, 80.98; H, 6.37; N, 5.90. Found: C, 80.90; H, 6.47; N, 5.91.
Spectroscopic data of 5: 1H NMR (CDCl3, 300 MHz): δ 1.75 (m, 4 H), 2.56 (broad s, 2 H), 2.73 (broad s, 2 H), 2.82 (t, 2 H, J = 7.7 Hz), 3.89 (s, 3 H), 4.08 (t, 2 H, J = 7.7 Hz), 6.89 (d, 1 H, J = 2.2 Hz), 7.40 (d, 1 H, J = 2.6 Hz). 13C NMR (CDCl3, 75 MHz): δ 21.65, 21.72, 23.26, 24.26, 25.00, 48.44, 55.65, 107.0, 118.69, 118.71, 130.6, 137.2, 138.5, 146.3, 157.8, 161.5, 185.4. IR (KBr): 2933, 2862, 2840, 1640, 1623, 1601 cm-1. Mp 157-158 ºC. Anal. Calcd. for C17H17NO2: C, 76.38; H, 6.41; N, 5.24. Found: C, 76.03; H, 6.42; N, 5.26.
Spectroscopic data of 6: 1H NMR (CDCl3, 300 MHz): δ 1.00 (m, 1 H), 1.25 (m, 2 H), 1.40 (m, 1 H), 1.60 (m, 1 H), 1.70 (m, 2 H), 2.37 (m, 1 H), 2.61 (m, 2 H), 2.81 (s, 1 H), 2.91 (m, 1 H), 3.11 (dd, 1 H, J = 12.2 Hz, J′ = 4.6 Hz), 3.44 (m, 1 H), 3.87 (s, 3 H), 4.11 (s, 1 H), 6.78 (s, 1 H), 12.93 (s, 1 H). 13C NMR (CDCl3, 75 MHz): δ 24.07, 24.15, 26.49, 27.38, 29.36, 44.07, 45.18, 49.74, 57.65, 58.61, 116.1, 119.9, 125.3, 131.0, 148.6, 153.0, 207.6. IR (KBr): 3424, 2929, 2792, 2651, 1640, 1468, 1442, 1302, 1257, 1161, 1092, 1021 cm-1. Mp 213 ºC (decomp.). Anal. Calcd. for C17H21NO3. HCl. 1.4 H2O: C, 58.44; H, 6.87; N, 4.01. Found: C, 58.58; H, 6.58; N, 3.97.
Spectroscopic data of 8: 1H NMR (DMSO-d 6, 300 MHz): δ 2.00 (m, 2 H), 3.05 (m, 4 H), 7.33 (d, 1 H, J = 4.4 Hz), 7.70 (m, 2 H), 8.33 (dd, 1 H, J = 8.2 Hz, J′ = 1.3 Hz), 8.66 (d, 1 H, J = 4.5 Hz), 9.14 (dd, 1 H, J = 9.1 Hz, J′ = 1.4 Hz), 9.36 (s, 1 H). 13C NMR (DMSO-d 6, 75 MHz): δ 21.73, 24.28, 29.84, 112.9, 121.2, 122.3, 124.4, 125.0, 126.4, 128.1, 128.2, 131.0, 141.9, 144.3, 145.8, 145.9. IR (KBr): 3426, 2930, 2875, 2820, 1604, 1575, 1434, 1415, 1272, 1253, 1199, 1186, 1098 cm-1. Mp 200 ºC (decomp.). Anal. Calcd. for C16H13NO: C, 81.68; H, 5.57; N, 5.95. Found: C, 81.55; H, 5.34; N, 5.93.
Spectroscopic data of 10: 1H NMR (CDCl3, 300 MHz): δ 1.85 (broad s, 4 H), 2.71 (m, 2 H), 3.05 (m, 2 H), 3.25 (m, 4 H), 3.45 (s, 3 H), 3.91 (m, 1 H), 7.09 (d, 1 H, J = 4.3 Hz), 8.64 (d, 1 H, J = 4.4 Hz). 13C NMR (CDCl3, 75 MHz): δ 22.31, 22.36, 23.95, 25.02, 28.77, 35.02, 56.16, 74.13, 110.7, 119.5, 124.1, 128.4, 134.2, 141.9, 142.1, 146.4, 148.7. IR (KBr): 3433, 3074, 2939, 2859, 1620, 1597, 1524, 1490, 1452, 1407, 1382, 1333, 1277, 1206, 1170, 1043, 1014 cm-1. Mp 181-182 ºC. Anal. Calcd. for C17H19NO2: C, 75.81; H, 7.11; N, 5.20. Found: C, 75.78; H, 7.06; N, 5.05.
Spectroscopic data of 11: 1H NMR (DMSO-d 6, 300 MHz): δ 1.77 (broad s, 4 H), 1.90 (m, 2 H), 2.73 (broad s, 2 H), 2.91 (m, 4 H), 3.14 (broad s, 2 H), 7.08 (d, 1 H, J = 4.3 Hz), 8.49 (d, 1 H, J = 4.3 Hz), 8.62 (s, 1 H). 13C NMR (CDCl3, 75 MHz): δ 22.13, 22.70, 22.78, 24.11, 24.84, 25.21, 29.90, 114.3, 118.8, 124.4, 130.2, 133.1, 142.1, 144.3, 145.9, 149.1. IR (KBr): 3432, 2932, 2868, 1636, 1601, 1434, 1361, 1309, 1270, 1192, 1173, 1154, 1090, 1047 cm-1. Mp 160-161 ºC. Anal. Calcd. for C16H17NO: C, 80.30; H, 7.16; N, 5.85. Found: C, 80.05; H, 7.02; N, 5.81.
Spectroscopic data of 13: 1H NMR (CDCl3, 300 MHz): δ 3.27 (s, 3 H), 6.81 (s, 1 H), 7.51 (d, 1 H, J = 4.6 Hz), 7.79 (dd, 1 H, J = J′ = 6.9 Hz), 7.91 (dd, 1 H, J = J′ = 7.0 Hz), 8.15 (d, 1 H, J = 7.7 Hz), 9.01 (d, 1 H, J = 4.6 Hz), 9.03 (s, 1 H), 9.31 (d, 1 H, J = 8.4 Hz). 13C NMR (CDCl3, 75 MHz): δ 55.95, 110.5, 117.9, 120.5, 124.8, 126.6, 128.9, 130.8, 131.0, 132.5, 134.3, 134.4, 135.5, 144.8, 149.7, 156.0, 179.3. IR (KBr): 2932, 2857, 1653, 1614 cm-1. Mp 203 ºC (decomp.). Anal. Calcd. for C17H11NO2: C, 78.15; H, 4.24; N, 5.36. Found: C, 77.88; H, 4.16; N, 5.33.