Beilstein J. Org. Chem. 2018, 14, 1834–1839.
1CHarom), 8.18 (dd, JH,H = 7.6 Hz, JH,H = 1.1 Hz, 1CHarom) 294 (4.32), 487 (3.91); anal. calcd for C27H15ClO3S2 (486.99):
ppm; 13C NMR δ 35.2 (thiophen-2-yl-CH), 119.9, 125.3, 125.6, C, 66.59; H, 3.10; S, 13.17; found: C, 66.39; H, 3.07; S, 13.06.
126.7, 127.0, 127.1, 127.2, 128.8, 129.2, 133.5, 134.4
(12CHarom, C=CH), 128.5, 131.8, 132.1, 135.3, 137.2, 144.2, (4aSR,10aRS)-10a-Methyl-2,4-diphenyl-4H-benzo[g]thio-
144.3 (6Carom, C=CH), 180.6, 181.4 (2C=O) ppm; IR ν: 3075 chromene-5,10-(4aH,10aH)-dione (6): Yield: 145 mg (37%).
(w), 3031 (w), 1652 (vs, 2C=O), 1589 (s), 1571 (s), 1489 (m), Yellow-brown viscous oil; 1H NMR δ 1.94 (s, CH3), 3.76 (d,
1442 (m), 1420 (w), 1331 (m), 1289 (vs), 1220 (m), 1151 (m), JH,H = 4.8 Hz, 1CH), 4.18 (t, JH,H = 4.5 Hz, 1CH), 6.50 (d,
1103 (w), 1033 (w), 919 (w), 831 (m), 767 (m), 704 (s), JH,H = 4.3 Hz, 1CH), 7.08–7.12 (m, 1CH), 7.16–7.19 (m, 2CH),
695 (s) cm−1; UV–vis (CH2Cl2) λmax/nm (lg ε): 244 (4.50), 338 7.30–7.38 (m, 5CH), 7.54–7.57 (m, 2CH), 7.58–7.61 (m, 2CH),
(3.59), 463 (3.34); anal. calcd for C23H14O2S2 (386.49): C, 7.79–7.82 (m, 1CH), 7.91–7.93 (m, 1CH) ppm; 13C NMR
71.48; H, 3.65; S, 16.59; found: C, 71.48; H, 3.65; S 16.59. δ 26.4 (CH3), 42.7 (CH-Ph), 55.9 (Cq), 58.0 (CH-S), 120.0,
126.3, 126.8, 126.9, 127.3, 128.0, 128.5, 128.6, 129.5, 133.8,
4-Phenyl-2-(thiophen-2-yl)-4H-benzo[g]thiochromene-5,10- 134.2 (14CHarom, C=CH), 132.4, 134.4, 134.6, 138.9, 139.6
dione (4c): Yield: 355 mg (92%). Red-orange crystals; (4Carom, C=CH), 193.9, 194.2 (2C=O) ppm; IR ν: 3062 (w),
mp 158 °C (dec.); 1H NMR δ 5.42 (d, JH,H = 6.5 Hz, Ph-CH), 3034 (w), 2957 (w), 1696 (vs) and 1691 (s, 2C=O), 1614 (s),
6.41 (d, JH,H = 6.5 Hz, C=CH), 7.01 (dd, JH,H = 5.2 Hz, 1489 (m), 1451 (m), 1266 (s), 1013 (m), 979 (m), 761 (s), 692
JH,H = 3.4 Hz, 1CHarom), 7.23–7.25 (m, 1CHarom), 7.28–7.33 (s) cm–1; ESIMS (for C26H20O2S): 395 (100, [M − 1]−).
(m, 3CHarom), 7.36 (dd, JH,H = 3.4 Hz, JH,H = 1.0 Hz,
1CHarom), 7.50–7.51 (m, 2CHarom), 7.69–7.75 (m, 2CHarom),
Supporting Information
8.09 (dd, JH,H = 7.4 Hz, JH,H = 1.3 Hz, 1CHarom), 8.14 (dd,
JH,H = 7.4 Hz, JH,H = 1.2 Hz, 1CHarom) ppm; 13C NMR δ 40.6
CCDC-1838975 contains the supplementary
(Ph-CH), 119.9, 125.3, 125.7, 126.6, 127.0, 127.6, 127.7, 128.4,
crystallographic data for this paper. These data can be
129.0, 133.4, 134.2 (12CHarom, C=CH), 125.9, 131.7, 132.1,
obtainded free of charge from the Cambridge
136.8, 140.3, 141.8, 143.9 (6Carom, C=CH), 180.6, 181.3
Crystallographic Data Centre via
(2C=O) ppm; IR ν: 3085 (w), 3063 (w), 1652 (vs, 2C=O), 1590
(s), 1573 (s), 1490 (m), 1453 (m), 1347 (m), 1335 (m), 1289
Supporting Information File 1
(vs), 1230 (m), 1150 (m), 1111 (w), 1074 (m), 839 (m), 880
(m), 815 (m), 710 (s), 696 (s) cm−1; UV–vis (CH2Cl2) λmax/nm
(lg ε): 269 (4.42), 473 (3.12); anal. calcd for C23H14O2S2
(386.49): C, 71.48; H, 3.65; S, 16.59; found: C, 71.48; H, 3.70;
S, 16.58.
Experimental data for selected compounds 4, details of the
crystal structure determination, and copies of 1H and
13C NMR spectra for all products.
11-Chloro-6-hydroxy-4-phenyl-2-(thiophen-2-yl)-4H-
naphtho[2,3-g]thiochromene-5,12-dione (4k): Yield: 285 mg
(59%). Dark red crystals; mp 162 °C (dec.); 1H NMR δ 5.78 (d, Acknowledgements
JH,H = 6.7 Hz, thiophen-2-yl-CH), 6.48 (d, JH,H = 6.8 Hz, Financial support by the National Science Center (NCN,
C=CH), 6.96 (dd, JH,H = 4.9 Hz, JH,H = 3.8 Hz, 1CHarom), Poland) in the framework of the Maestro-3 grant (2012/06A/
7.01–7.11 (m, 2CHarom), 7.21 (dd, JH,H = 4.9 Hz, ST5/00219) is gratefully acknowledged.
JH,H = 1.0 Hz, 1CHarom), 7.35 (dd, JH,H = 4.9 Hz,
ORCID® iDs
JH,H = 1.0 Hz, 1CHarom), 7.40 (dd, JH,H = 4.9 Hz,
JH,H = 1.0 Hz, 1CHarom), 7.76–7.80 (m, 1CHarom), 7.87–7.89
(m, 1CHarom), 8.59 (d, JH,H = 8.2 Hz, 1CHarom), 8.63 (d,
JH,H = 8.2 Hz, 1CHarom), 14.98 (s, OH) ppm; 13C NMR δ 34.5
(thiophen-2-yl-CH), 118.7, 125.0, 125.5, 125.7, 125.8, 126.2,
127.2, 127.5, 127.8, 130.1, 132.2 (10CHarom, C=CH), 108.8,
References
1. Boger, D. L.; Weinreb, S. N., Eds. Hetero Diels–Alder Methodology in
122.5, 127.6, 128.5, 134.8, 135.2, 139.9, 143.5, 142.1, 147.4,
162.6 (10Carom, C=CH), 179.0, 184.0 (2C=O) ppm; IR ν: 3022
Organic Synthesis; Organic Chemistry, A Series of Monographs;
(w), 2953 (s), 2923 (w), 1655 (s, 2C=O), 1601 (s), 1584 (s),
Academic Press Inc.: London, 1987; Vol. 47.
1565 (s), 1491 (m), 1427 (s), 1397 (s), 1360 (s), 1360 (m), 1333
2. Blond, G.; Gulea, M.; Mamane, V. Curr. Org. Chem. 2016, 20,
(m), 1242 (vs), 1170 (m), 902 (s), 852 (m), 832 (m), 758 (m),
699 (vs) cm−1; UV–vis (CH2Cl2) λmax/nm (lg ε): 245 (4.69),
1838