438 P. Cheng et al.
in ppm and Hz, respectively. e mass spectra were
recorded on an Esquire 3000 LC-MS mass spectrometer.
Elemental analyses were performed with a MOD-1106
instrument and were consistent with theoretical values
within 0.4%. TLC analysis was carried out on silica
gel plates GF254 (Qindao Haiyang Chemical, China).
Flash column chromatography was carried out on silica
gel 300–400 mesh. Anhydrous solvent and reagents
were all analytical pure and dried through routine
protocols.
H]. Anal. calcd. for C17H10O4: C, 73.38; H, 3.62. Found: C,
73.47; H, 3.63.
9,11-dibromo-8,10-dihydroxy-7H-benzo[c]xanthen-7-one(2)
1H NMR (500 MHz, CDCl3) δ 7.70 (m, 3H), 7.91 (m, 1H),
8.16 (d, J= 8.7 Hz, 1H), 8.74 (m, 1H), 13.97 (s, 1H). ESI-MS:
m/z, 435.62 [M - H]. Anal. calcd. for C17H8Br2O4: C, 46.83;
H, 1.85. Found: C, 46.70; H, 1.85.
8,10-dihydroxy-9,11-diiodo-7H-benzo[c]xanthen-7-one(3)
1H NMR (500 MHz, DMSO) δ 7.80 (m, 1H), 7.87 (m, 2H),
8.00 (m, 1H), 8.07 (m, 1H), 8.62 (m, 1H), 10.85 (br s, 1H).
ESI-MS: m/z, 529.22 [M - H]. Anal. calcd. for C17H8I2O4: C,
38.52; H, 1.52. Found: C, 38.64; H, 1.52.
General procedure for the synthesis of the
benzoxanthone analogues
8,10-dihydroxy-7H-benzo[c]xanthen-7-one is synthe-
sized as shown in Scheme 1. We treated 1,3,5-trihydroy-
benzene with 1 equiv. of 1-naphthol-2-carboxylic acid in
phosphorus oxychloride at 70°C. e desired product 18
was obtained in 35.8% yield after a reaction time of 6 h.
As depicted in Scheme 2, starting from 8,10-dihydroxy-7-
H-benzoxanthen-7-one (1), we carried out modification
to prepare a variety of novel benzoxanthone analogues
with different side chain. Treated 1 with Br2 in acetic
acid at room temperature to produce bromide deriva-
tive 2 or 49. And treated 1 with NIS in DMF at room tem-
perature to produce iodides derivative 310. Treatment of
compound 1 with 2-hydroxybenzyl alcohol and ZnCl2 in
dioxane solution at 100°C for 6 h gives derivative 511. On
treatment of compound 1 with different acyl chloride
provided 6a–c12. e target compound 7a was prepared
from 1, which was treated with benzyl bromide and
K2CO3 in the presence of acetone at reflux for 4 h. en
the 8-hydroxyl of 7a was esterified with corresponding
acyl chloride to give the compounds 7b–d13. And 8,10-
dihydroxyl of 1 were esterified with corresponding acyl
chloride to give the compound 7e (Scheme 2). e struc-
5,9,11-tribromo-8,10-dihydroxy-7H-benzo[c]xanthen-7-
one(4)
1H NMR (500 MHz, CDCl3) δ 7.60 (m, 1H), 7.73 (m, 1H),
8.08 (s, 1H), 8.16 (d, J= 8.4 Hz, 1H), 8.45 (d, J= 8.3 Hz, 1H),
11.93 (s, 1H). ESI-MS: m/z, 514.65 [M + H]. Anal. calcd.
for C17H7Br3O4: C, 39.65; H, 1.37. Found: C, 39.59; H, 1.37.
8,10-dihydroxy-9,11-bis(2-hydroxybenzyl)-7H-benzo[c]
xanthen-7-one(5)
1H NMR (500 MHz, DMSO) δ 13.23 (s, 1H),10.02(br s,3H),
8.54 (s, 1H), 8.04 (m,2H), 7.90 (m,1H), 7.80 (m,1H), 7.73
(m,1H), 7.68 (m,2H), 6.90 (m,4H), 6.67 (m,1H), 6.58
(m,1H), 4.29 (s, 2H), 3.96 (s, 2H). ESI-MS: m/z, 489.30 [M
- H]. Anal. calcd. for C31H22O6: C, 75.91; H, 4.52. Found: C,
75.77; H, 4.53.
8-hydroxy-7-oxo-7H-benzo[c]xanthen-10-yl acetate(6a)
1H NMR (500 MHz, CDCl3) δ 2.37 (s, 3H), 6.63 (d, J= 2 Hz,
1H), 7.00 (d, J= 2 Hz, 1H), 7.74 (m, 3H), 7.92 (m, 1H), 8.21
(m, 1H), 8.61 (m, 1H), 12.90 (s, 1H). ESI-MS: m/z, 319.60
[M - H], 321.25 [M + H]. Anal. calcd. for C19H12O5: C, 71.25;
H, 3.78. Found: C, 71.33; H, 3.78.
1
tures of target compounds were confirmed by H NMR
data and 13C NMR.
e synthesized compounds are listed in Schemes 1
and 2 and the obtained spectral data are as follows:
8-hydroxy-7-oxo-7H-benzo[c]xanthen-10-yl isonicotinate(6b)
1H NMR (500 MHz, CDCl3) δ 6.76 (d, J= 2 Hz, 1H), 7.12 (d,
J= 2 Hz, 1H), 7.72 (m, 3H), 7.92 (m, 1H), 8.17 (m, 2H), 8.21
(m, 1H), 8.59 (m, 1H), 8.92 (m, 2H), 12.97 (s, 1H). ESI-MS:
m/z, 384.60 [M + H]. Anal. calcd. for C23H13NO5: C, 72.06;
H, 3.42; N, 3.65. Found: C, 72.11; H, 3.43; N 3.64.
8,10-dihydroxy-7H-benzo[c]xanthen-7-one(1)
1H NMR (500 MHz, CDCl3), δ 12.91 (s, 1H), 10.24 (s, 1H),
8.62 (d, J= 7.9 Hz, 1H), 8.14 (d, J= 8.7 Hz, 1H), 7.94 (d,
J= 7.9 Hz, 1H), 7.72 (m, 3H), 6.60 (d, J= 1.9 Hz, 1H), 6.36
(d, J= 1.9 Hz, 1H). 13C NMR (500 MHz, DMSO-d6), δ 94.79,
99.00, 103.14, 115.86, 120.15, 122.87, 123.29, 124.52,
127.89, 128.61, 130.45, 136.48, 153.29, 157.45, 162.88,
165.89, 179.95. ESI-MS: m/z, 277.90 [M - H], 279.95 [M +
8-hydroxy-7-oxo-7H-benzo[c]xanthen-10-yl nicotinate(6c)
1H NMR (500 MHz, CDCl3) δ 6.78 (d, J = 2 Hz, 1H),
7.14 (d, J = 2 Hz, 1H), 7.52 (m, 1H), 7.75 (m, 3H), 7.92
Scheme 1. Reagents and conditions: (a) POCl3, 70°C.
Journal of Enzyme Inhibition and Medicinal Chemistry