2098
Med Chem Res (2013) 22:2093–2104
1278, 718 cm-1; H NMR (DMSO-d6) d 12.00 (1H, br.s,
2-OH), 8.24 (1H, s, H-1), 8.17–8.15 (2H, m, H-5 &H-8),
7.92–7.90 (2H, m, H-6 & H-7), 7.65 (1H, s, H-4); 13C
NMR (DMSO-d6) d 182.8 (C-10), 181.2 (C-9), 160.4
(C-2), 135.4 (C-6), 135.0 (C-7), 134.8 (C-13), 133.7
(C-11), 133.6 (C-12), 132.9 (C-1), 127.4 (C-5 & C-8),
126.6 (C-14), 117.5 (C-3), 113.5 (C-4); MS m/z (rel. int.)
304 ([M ? 2]?, 98), 302 (M?, 100), 276 (19), 274 (18),
248 (17), 246 (18), 223 (15), 195 (18), 167 (21), 139 (89),
123 (14), 83 (36), 69 (94), 50 (25).
of organic compounds (1965)]; UV (MeOH) kmax 366, 277,
243 nm; IR (KBr disc) m 3393 (OH), 1655 (C=O, unch-
elated), 1576 (C=C, aromatic), 1329, 1290, 1245,
715 cm-1; 1H NMR (DMSO-d6) d 11.50 (1H, br.s, 3-OH),
8.16–8.11 (2H, m, H-5 & H-8), 7.93–7.86 (2H, m, H-6 &
H-7), 7.59 (1H, d, J = 2.5 Hz, H-4), 7.46 (1H, d,
J = 2.5 Hz, H-2); 13C NMR (DMSO-d6) d 182.3 (C-10),
180.6 (C-9), 162.6 (C-3), 138.2 (C-14), 135.5 (C-6), 134.8
(C-11), 134.5 (C-7), 132.8 (C-12), 128.1 (C-2), 127.6
(C-5), 126.9 (C-8), 124.2 (C-1), 122.9 (C-13), 114.3 (C-4);
MS m/z (rel. int.) 304 ([M ? 2]?, 22), 302 (M?, 24), 276
(11), 274 (11), 248 (8), 246 (9), 223 (6), 195 (14), 167 (17),
139 (100), 113 (13), 87 (12), 69 (23), 50 (38).
1
1-Hydroxyanthraquinone (4) Yellow-orange needles; mp
190–191 °C [lit. 195–196 °C, Dictionary of Natural Prod-
ucts (2003)]; UV (CHCl3) kmax 405, 330, 270, 253 nm; IR
(KBr disc) m 3436 (OH), 1674 (C=O, unchelated), 1638
(C=O, chelated), 1592 (C=C, aromatic), 1452, 1259, 1227,
1,3-Dihydroxyanthraquinone or xanthopurpurin (7)
When phthalic anhydride (6.7 g, 45 mmol) and resorcinol
(4.51 g, 41 mmol) were used as starting material, two
products 7 (0.98 g, 11 %) and 3,3-di(20,40-dihydroxy-
phenyl)phthalide (2.29 g, 31 %) were found with total
yield of 42 %.
762 cm-1 1H NMR (CDCl3) d 12.64 (1H, s, 1-OH),
;
8.35–8.32 (2H, m, H-5 & H-8), 7.86 (1H, dd, J = 7.5 &
1.0 Hz, H-4), 7.85–7.83 (2H, m, H-6 & H-7), 7.71 (1H, t,
J = 8.0 & 7.5 Hz, H-3), 7.34 (1H, dd, J = 8.0 & 1.0 Hz,
H-2); 13C NMR (CDCl3) d 188.9 (C-9), 182.7 (C-10),
162.8 (C-1), 137.0 (C-3), 134.9 (C-7), 134.4 (C-6), 133.9
(C-12), 133.7 (C-14), 133.5 (C-11), 127.7 (C-8), 127.2
(C-5), 124.6 (C-2), 119.8 (C-4), 116.4 (C-13); MS m/z (rel.
int.) 224 (M?, 100), 196 (19), 168 (36), 139 (51), 113 (7),
98 (10), 84 (13), 70 (44), 50 (19).
1,3-Dihydroxyanthraquinone or xanthopurpurin (7) Yel-
low amorphous compound; mp 268 °C [lit. 268–270 °C,
Dictionary of Natural Products (2003)]; UV (MeOH) kmax
413, 280, 241 nm; IR (KBr disc) m 3394 (OH), 1630
(C=O), 1340, 1320, 1161, 779, 712 cm-1 1H NMR
;
(DMSO-d6) d 12.75 (1H, s, 1-OH), 11.35 (1H, br.s, 3-OH),
8.22–8.15 (2H, m, H-5 & H-8), 7.95–7.89 (2H, m, H-6 &
H-7), 7.16 (1H, d, J = 2.0 Hz, H-4), 6.63 (1H, d,
J = 2.0 Hz, H-2); MS m/z (rel. int.) 240 (M?, 100), 212
(17), 184 (27), 155 (10), 128 (21), 106 (11), 92 (11), 77
(17), 69 (21), 51 (23).
2-Hydroxyanthraquinone (5) Yellow amorphous solid;
mp 298–299 °C [lit. 302–303 °C, dictionary of natural
products (2003)]; UV (MeOH) kmax 373, 329, 270,
242 nm; IR (KBr disc) m 3370 (OH), 1672 (C=O, unch-
elated), 1578 (C=C, aromatic), 1341, 1305, 1281,
720 cm-1; 1H NMR (DMSO-d6) d 11.08 (1H, br.s, 2-OH),
8.18-8.16 (2H, m, H-5 & H-8), 8.10 (1H, d, J = 8.5 Hz,
H-4), 7.91–7.88 (2H, m, H-6 & H-7), 7.51 (1H, d,
J = 2.5 Hz, H-1), 7.25 (1H, dd, J = 8.5 & 2.5 Hz, H-3);
13C NMR (DMSO-d6) d 183.4 (C-9), 181.9 (C-10), 163.8
(C-2), 135.9 (C-13), 135.3 (C-7), 134.7 (C-6), 133.9
(C-12), 133.8 (C-11), 130.6 (C-4), 127.3 (C-8), 127.2
(C-5), 125.9 (C-14), 122.3 (C-3), 112.9 (C-1); MS m/z (rel.
int.) 224 (M?, 100), 196 (35), 168 (35), 139 (78), 113 (9),
98 (7), 84 (12), 63 (21).
1,4-Dihydroxyanthraquinone or quinizarin (8)
Reaction between phthalic anhydride (6.7 g, 45 mmol) and
hydroquinone (4.51 g, 41 mmol) produced 8 (4.33 g) with
44 % yield.
1,4-Dihydroxyanthraquinone or quinizarin (8) Orange-
red crystals; mp 197–198 °C [lit. 194 °C, Dictionary of
Natural Products (2003)]; UV (CHCl3) kmax 476, 328, 280,
250 nm; IR (KBr disc) m 3437 (OH), 2926, 1630 (C=O,
chelated), 1591 (C=C, aromatic), 1453, 1358, 1257, 1226,
1-Bromo-3-hydroxyanthraquinone (6)
790 cm-1 1H NMR (CDCl3) d 12.92 (2H, s, 1-OH &
;
Reaction between phthalic anhydride (6.7 g, 45 mmol) and
3-bromophenol (7.05 g, 41 mmol) gave four products
including 1 (3.96 g, 32 %), 2 (0.12 g, 1 %), 4 (0.46 g,
5 %) and 6 (1.36 g, 11 %). The total yield was 49 %.
4-OH), 8.37–8.35 (2H, m, H-5 & H-8), 7.86–7.85 (2H, m,
H-6 & H-7), 7.33 (2H, s, H-2 & H-3); 13C NMR (CDCl3) d
187.2 (C-9 & C-10), 158.1 (C-1 & C-4), 134.8 (C-6 &
C-7), 133.7 (C-11 & C-12), 129.6 (C-2 & C-3), 127.3 (C-5
& C-8), 113.0 (C-13 & C-14); MS m/z (rel. int.) 240
(M?, 100), 212 (10), 183 (17), 155 (11), 128 (14), 102 (11),
77 (6).
1-Bromo-3-hydroxyanthraquinone (6) Yellow amor-
phous compound; mp 180–181 °C [lit. 187 °C, dictionary
123