An Expedient Synthesis of Unusual Oxoisoaporphine and Annelated Quinoline Derivatives

Eduardo Sobarzo-Sánchez; Bruce K. Cassels; Luis Castedo

doi:10.1055/s-2003-41422

LETTER

An Expedient Synthesis of Unusual Oxoisoaporphine and Annelated Quinoline Derivatives

Eduardo Sobarzo-Sánchez*^a, Bruce K. Cassels^a, Luis Castedo^b
^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

Abstract

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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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References

For further information on the photo- and electrochemical properties of azabenzanthrones, see:

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8

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.

9 Sobarzo-Sánchez E. Cassels BK. Jullian C. Castedo L. Magn. Reson. Chem. 2003, 41: 545

10 Kunitomo J.-I. Miyata Y. Heterocycles 1986, 24: 437