Russ. J. Org. Chem. 2010, 46, 1192-1206 (Zhurnal Organicheskoi Khimii, 2010, 46, 1191-1204) (original) (raw)

Partly hydrogenated 2-[5-methyl(bromo, nitro)furan-2-yl]-substituted furo [3,2-c]quinolines, pyrano-[3,2-c]quinolines, and 4-ethoxyquinolines were synthesized by the imino Diels-Alder (Povarov) reaction. Cycloadditions of these compounds with maleic, citraconic, and dibromomaleic anhydrides, as well as with acryloyl, methacryloyl, and cinnamoyl chlorides led to the formation of substituted epoxyisoindolo[2,1-a]quinolines and -quinolinecarboxylic acids. Oxidation of the double C=C bond in the adducts, esterification of the carboxy group, and aromatization of the 7-oxabicycloheptene fragment were accomplished. s (3H, COMe), 2.97 d.d.q (1H, 3a-H, J 3a, 4 = 3.2, J 3a, 9b = 7.6, J 3a, 3 = 8.2 Hz), 3.74 d.t -H, 2 J = 3 J = 8.6 Hz), 3.82 q (1H, 2-H, 2 J = 8.4, 3 J = 4.4 Hz), 4.44 br.s (NH), 4.81 d (1H, 4-H, J 3a, 4 = 3.2 Hz), 5.22 d (1H, 9b-H, J 3a, 9b = 7.6 Hz), 6.30 d.d (1H, 3′-H, 4 J = 0.8, 3 J = 3.2 Hz), 6.38 d.d (1H, 4′-H, J 5′, 4′ = 1.8, J 4′, 3′ = 3.2 Hz), 6.59 d (1H, 6-H, J 6, 7 = 8.5 Hz), 7.40 d.d (1H, 5′-H, J 5′, 4′ = 1.8, J 5′, 3′ = 0.8 Hz), 7.74 d.d (1H, 7-H, J 7, 9 = 2.0, J 6, 7 = 8.5 Hz), 7.97 d (1H, 9-H, J 7, 9 = 2.0 Hz). Mass spectrum, m/z (I rel , %): 283 (100) [M] + , 268 (22), 254 (13), 238 (90), 210 (9), 198 (6), 172 (15), 167 (5), 103 (5), 81 (6), 43 (7). Found, %: C 72.31; H 6.21; N 4.78. C 17 H 17 NO 3 . Calculated, %: C 72.07; H 6.05; N 4.94. M 283.12. 1-H), 2.05 m (1H, 1-H), 2.34 d.d.d (1H, exo-10-H, J 9a, exo-10 = 3.9, J exo-10, 11 = 4.8, 2 J = 12.1 Hz), 2.76 d.d (1H, 9a-H, J 9a, exo-10 = 3.9, J 9a, endo-10 = 9.2 Hz), 3.21 m (1H, 13c-H), 3.89-4.03 m (2H, 2-H), 4.47 d (1H, 13b-H, J 13b, 13c = 3.4 Hz), 5.17 d.d (1H, 11-H, J exo-10, 11 = 4.8, J 11, 12 = 1.5 Hz), 5.37 d (1H, 3a-H, J 3a, 13c = 8.2 Hz), 6.47 d.d (1H, 12-H, J 11, 12 = 1.5, J 12, 13 = 5.8 Hz), 6.57 d (1H, 13-H, J 12, 13 = 5.8 Hz), 6.98 d.d (1H, 6-H, J 5, 6 = 7.7, J 4, 6 = 1.5 Hz), 7.21 t (1H, 5-H, J 4, 5 = J 5, 6 = 7.7 Hz), 7.22 d.d (1H, 4-H, J 4, 5 = 7.7, J 4, 6 = 1.5 Hz), 9.45 s (OH); cis isomer: 1.77 d.d (1H, endo-10-H, J 9a, endo-10 = 9.2, 2 J = 11.6 Hz), 1.90 m (1H, 1-H), 2.13 m (1H, 1-H), 2.17 d.d.d (1H, exo-10-H, J 9a, exo-10 = 3.9, J exo-10, 11 = 4.4, 2 J = 11.6 Hz), 2.55 d.d (1H, 9a-H, J 9a, exo-10 = 3.9, J 9a, endo-10 = 9.2 Hz), 3.15 m (1H, 13c-H), 3.89-4.03 m (2H, 2-H), 4.52 d (1H, 13b-H, J 13b, 13c = 2.9 Hz), 5.14 d.d (1H, 11-H, J exo-10, 11 = 4.4, J 11, 12 = 1.5 Hz), 5.35 d (1H, 3a-H, J 3a,13c = 8.2 Hz), 6.53 d.d (1H, 12-H, J 11, 12 = 1.5, J 12, 13 = 5.8 Hz), 6.58 d (1H, 13-H, J 12, 13 = 5.8 Hz), 7.00 d.d (1H, 6-H, J 5, 6 = 7.7, J 4, 6 = 1.5 Hz), 7.29 t (1H, 5-H, J 4, 5 = J 5, 6 = 7.7 Hz), 7.36 d.d (1H, 4-H, J 4, 5 = 7.7, J 4, 6 = 1.5 Hz), 9.45 s (OH). Mass spectrum, m/z (I rel , %): 311 (31) [M] + , ,13b,13c-hexahydro-3aH-furo[3,2-c]isoindolo[2,1-a]quinolin-9(9aH)-one (VIIId) (mixture of trans and cis isomers at a ratio of 1 : 1. Yield 87%, mp 157-158°C (from hexane-ethyl acetate), R f 0.62, 0.91 (hexane-ethyl acetate, 1 : 1). IR spectrum: ν 1691 cm -1 (C=O). 1 H NMR spectrum (CDCl 3 ), δ, ppm: trans isomer: 1.69 s (3H, Me), 1.80 d.d (1H, endo-10-H, J 9a, endo-10 = 9.0, 2 J = 11.8 Hz), 1.86 m (1H, 1-H), 2.07 d.d (1H, exo-10-H, J 9a, exo-10 = 3.5, 2 J = 11.8 Hz), 2.65 m (1H, 1-H), 2.89 m (1H, 13c-H), 3.72 d.d (1H, 9a-H, J 9a, exo-10 = 3.5, J 9a, endo-10 = 9.0 Hz), 3.86-3.95 m (2H, 2-H), 4.42 d (1H, 13b-H, J 13b, 13c = 2.7 Hz), 5.36 d (1H, 3a-H, J 3a,13c = 8.2 Hz), 6.33 d ( 1H, J 12, 13 = 5.7 Hz), 6.54 d (1H, J 12, 13 = 5.7 Hz), 7.17 d.t (1H, J 4, 5 = J 5, 6 = 7.7, J 5, 7 = 1.1 Hz), 7.32 d.d (1H, J 5, 6 = 7.7, J 6, 7 = 8.1 Hz), 7.42 br.d (1H, J 4, 5 = 7.7 Hz), 8.03 d.d (1H, J 5, = 1.1, J 6, 7 = 8.1 Hz); cis isomer: 1.64 s (3H, Me), 1.71 d.d (1H, endo-10-H, J 9a, endo-10 = 8.7, 2 J = 11.8 Hz), 1.86 m (1H, 1-H), 1.99 d.d (1H, exo-10-H, J 9a, exo-10 = 3.6, 2 J = 11.8 Hz), 2.70 m (1H, 1-H), 3.11 m (1H, 13c-H), 3.66 d.d (1H, 9a-H, J 9a, exo-10 = 3.6, J 9a, endo-10 = 8.7 Hz), 3.84 m (2H, 2-H), 4.70 d (1H, 13b-H, J 13b, 13c = 2.5 Hz), 5.24 d (1H, 3a-H, J 3a, 13c = 7.2 Hz), 6.30 d (1H, 13-H, J 12, 13 = 5.7 Hz), 6.44 d (1H, 12-H, J 12, 13 = 5.7 Hz), 7.11 d.t (1H, 5-H, J 4, 5 = J 5, 6 = 7.7, J 5, 7 = 1.1 Hz), 7.24 d.d (1H, 6-H, J 5, 6 = 7.7, J 6, 7 = 8.4 Hz), 7.48 br.d (1H, 4-H, J 4, 5 = 7.7 Hz), 8.66 d.d (1H, 7-H, J 5, 7 = 1.1, J 6, 7 = 8.4 Hz). Mass spectrum, m/z (I rel , %): 309 (18) [M] + ,