The Journal of Organic Chemistry
Page 8 of 13
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7a-hydroxy-12-oxo-13-(o-tolyl)-7a,12,12a,13-tetrahydrobenzo[f]indeno[1,2-b]chromene-3-carbonitrile:
(3ae)
Yield: 80% (166 mg), yellow solid; mp: 201.4ꢀ205.2°C; IR (KBr) νmax: 2225, 1718, 1645, 1381, 1218, 998,
824, 762, 530, cmꢀ1; 1H NMR (400 MHz, DMSOꢀd6) δ =8.45 (s, 1H), 8.23 (s, 1H), 8.13 (d, J = 7.2 Hz, 1H),
7.92 – 7.87 (m, 2H), 7.64 (d, J = 8.0 Hz, 3H), 7.58 (d, J = 7.2 Hz, 1H), 7.29 (d, J = 6.4 Hz, 1H), 7.22 (d, J =
8.8 Hz, 1H), 7.09 (t, J = 6.6 Hz 1H), 6.94 (t, J = 6.8 Hz 1H), 6.71 (d, J = 6.8 Hz, 1H), 5.48 (s, 1H), 3.61 (s,
1H), 2.73 (s, 3H);13C NMR (100 MHz, DMSOꢀd6) δ= 199.3, 152.8, 152.6, 139.8, 136.0, 134.9, 134.5, 133.0,
130.5, 130.2, 130.0, 128.2, 127.7, 127.5, 126.4, 125.6, 123.5, 123.2, 122.3, 120.4, 119.0, 115.7, 106.0, 101.7,
57.5, 32.8, 19.2; HRMS (ESI): m/z [M+Na]+ calcd for: C28H19NNaO3: 440.1257; found: 440.1260.
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7a-hydroxy-12-oxo-13-(o-tolyl)-7a,12,12a,13-tetrahydrobenzo[f]indeno[1,2-b]chromene-3-carbaldehyd
e: (3af)
Yield: 83% (174 mg), yellow solid; mp: 172.3ꢀ175.6°C; IR (KBr) νmax: 2554, 1647, 1385, 999, 826, 765,
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626 cmꢀ1; H NMR (600 MHz, DMSOꢀd6) δ= 10.05 (s, 1H), 8.48 (s, 1H), 8.21 (s, 1H), 8.13 (d, J = 6.0 Hz,
1H), 8.02 (d, J = 8.4 Hz, 1H), 7.89 (s, 1H), 7.83 (d, J = 7.2 Hz, 1H), 7.67 – 7.64 (m, 2H), 7.60 (d, J = 5.4 Hz,
1H), 7.31 (d, J = 6.0 Hz, 1H), 7.20 (d, J = 8.4 Hz, 1H), 7.11 (s, 1H), 6.95 (s, 1H), 6.72 (s, 1H), 5.49 (s, 1H),
3.58 (s, 1H), 2.73 (s, 3H); 13C NMR (150 MHz, DMSOꢀd6) δ= 199.8, 153.2, 153.0, 140.2, 136.2, 135.2, 134.8,
133.3, 132.0, 131.3, 130.8, 130.5, 128.6, 128.0, 126.7, 125.7, 124.0, 123.4, 122.6, 120.2, 120.0, 116.3, 101.9,
57.6, 33.0, 32.9, 19.2; HRMS (ESI): m/z [M+Na]+ calcd for: C28H20NaO4: 443.1254; found: 443.1249.
3-acetyl-7a-hydroxy-13-(o-tolyl)-12a,13-dihydrobenzo[f]indeno[1,2-b]chromen-12(7aH)-one: (3ag)
Yield: 81% (175 mg), yellow solid; mp: 219.4ꢀ221.8°C; IR (KBr) νmax: 1710, 1623, 1469, 1280, 1122, 989,
720, 557 cmꢀ1; 1H NMR (600 MHz, DMSOꢀd6) δ= 8.54 (s, 1H), 8.17 (s, 1H), 8.13 (d, J = 7.2Hz, 1H), 8.00 (d,
J = 8.4 Hz, 1H), 7.92– 7.89 (m, 2H), 7.64 (d, J = 6.6 Hz, 2H), 7.59 (s, 1H), 7.30 (d, J = 6.0 Hz, 1H), 7.16 (d,
J = 8.4 Hz, 1H), 7.11 (s, 1H), 6.95 (s, 1H), 6.74 (d, J = 6.6 Hz, 1H), 5.49 (s, 1H), 3.86 (s, 3H), 3.57 (s, 1H),
2.74 (s, 3H); 13C NMR (150 MHz, DMSOꢀd6) δ= 199.9, 166.2, 153.3, 152.4, 140.2, 136.2, 135.1, 133.8,
133.3, 131.0, 130.9, 130.6, 128.5, 128.0, 126.6, 126.1, 124.8, 123.4, 122.8, 122.4, 119.7, 116.0, 101.9, 57.7,
52.1, 33.0, 32.9, 19.1; HRMS (ESI) m/z calcd for C29H23O5+ (M+H)+ 451.1540, found 451.1534.
3-bromo-7a-hydroxy-13-(o-tolyl)-12a,13-dihydrobenzo[f]indeno[1,2-b]chromen-12(7aH)-one: (3ah)
Yield: 83% (195 mg), white solid; mp: 221.7ꢀ224.2°C; IR (KBr) νmax: 1708, 1589, 1221, 1122, 1084, 753,
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688, 567 cmꢀ1; H NMR (600 MHz, DMSOꢀd6) δ= 8.18 (d, J =7.8 Hz 1H), 8.11 (s, 1H), 7.89 (t, J = 7.2 Hz,
1H), 7.78 (d, J = 8.4 Hz, 1H), 7.67 (d, J = 7.2 Hz, 1H), 7.59ꢀ7.53 (m, 3H), 7.30 (d, J = 7.2 Hz, 1H), 7.16 (d,
J = 8.4 Hz, 1H), 7.11 (t, J = 7.2 Hz, 1H), 6.97 (t, J = 6.6 Hz, 1H), 6.79 (d, J = 7.8 Hz, 1H), 5.50 (s, 1H), 3.59
(s, 1H), 2.75 (s, 3H); `13C NMR (150 MHz, DMSOꢀd6) δ= 200.0, 153.4, 150.7, 140.3, 136.2, 135.1, 133.4,
130.8, 130.3, 130.2, 130.1, 128.7, 128.0, 127.9, 126.6, 123.5, 123.4, 122.5, 122.4, 120.2, 120.0, 117.0, 116.2,
101.8, 57.9, 33.2, 33.1, 19.2; HRMS (ESI): m/z [M+Na]+ calcd for: C27H19BrNaO3: 493.0410; found:
493.0419.
2-bromo-7a-hydroxy-13-(o-tolyl)-12a,13-dihydrobenzo[f]indeno[1,2-b]chromen-12(7aH)-one: (3ai)
Yield: 87% (204 mg), yellow solid; mp: 161.7ꢀ164.0°C; IR (KBr) νmax: 1708, 1619, 1338, 1123, 1080, 825,
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748, 602cmꢀ1; H NMR (600 MHz, DMSOꢀd6) δ= 8.09 (s, 1H), 8.04 (s, 1H), 7.83 (s, 1H), 7.74 (s, 2H), 7.59
(s, 2H), 7.54 (s, 1H), 7.41 (d, J =7.2 Hz, 1H), 7.29 (s, 1H), 7.11 (s, 1H), 7.06 (d, J = 8.4 Hz, 1H), 6.95 (s,
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