and irradiation experiments, on CDCl solutions unless other- 1,3-Dihydroxy-6-(2-amino-2-oxoethoxy)-7-methoxy-2,8-bis(3-me-
3
wise stated, were measured with a Bruker AC-200 (200 MHz) thylbut-2-enyl)-9H-xanthen-9-one (9): m.p. 231±233 8C; UV:
spectrometer. The chemical shifts are recorded in terms of ppm lmax (log e) = 245 (4.48), 263 (4.47), 315 (4.29) nm; IR:
±1
1
with tetramethylsilane as internal reference. Mass spectra were nmax = 3370 (b), 3184 (b), 1661, 1609, 1585 cm ; H-NMR:
determined with an AEI-MS-902 spectrometer (at 70 eV). Pre- d = 1.68 (3H, s, H-5¢), 1.76 (3H, s, H-5¢¢), 1.84 (6H, s, H-4¢, H-4¢¢),
coated silica gel 60 GF254 (Merck; Darmstadt, Germany) was 3.48 (2H, d, J = 7 Hz, H-1¢), 3.82 (3H, s, 7-OCH ), 4.15 (2H, d,
3
used for thin layer chromatography. Merck silica gel 70±250 J = 7 Hz, H-1¢¢), 5.23, (1H, bt, H-2¢), 5.27 (1H, bt, H-2¢¢), 6.42 (1H,
mesh was used for column chromatography.
s, 3-OH), 6.30 (1H, s, H-4), 6.75 (1H, s, H-5), 13.66 (1H, s, 1-OH),
substituent group: OCH CONH 4.62 (2H, s, OCH ), 5.70 and 6.75
2
2
2
Isolation of mangostin and the preparation of compounds 1±3, (2H, 2bs, NH ); MS: m/z = 467 (76), 424 (100), 412 (46), 396
2
5
±7, 12 ± 18, 21±22 and 29±32 have been previously reported (76), 368 (26); anal. calcd. for C H O N: C 66.8, H 6.3, N 3.0;
26 29 7
[16].
found: C 66.5, H 6.5, N 2.8.
Preparation of propanol derivative 4
Preparation of epoxide derivatives 10 and 11
A solution of mangostin (1.5 g, 3.6 mmol) in methanol (5 mL) was A solution of mangostin (5 g, 12 mmol) in dimethylformamide
added to a solution of sodium (230 mg) in methanol (5 mL). The (20 mL) and sodium hydride (2 g) in dimethylformamide (10
mixture was stirred for 15 minutes, then 3-chloropropanol (0.6 mL) was stirred at room temperature for 0.5 h. Then 1-chloro-
mL, 7 mmol) and sodium iodide (1.1 g, 7.1 mmol) were added. 2,3-epoxypropane (2.5 mL, 31 mmol) was added. The reaction
The reaction mixture was refluxed for 24 h and then worked up. mixture was refluxed for 6 h and then worked up. The residue
The crude product was chromatographed on silica gel and eluted was chromatographed on silica gel and eluted with light petro-
with dichloromethane/acetone (10:1) to obtain 4 as a solid; leum/dichloromethane (4:5) to give yellow needles of 10 (yield:
yield: 380 mg(22%).
0.2 g, 3%) and 11 (yield: 1.5 g, 26%).
1
,3-Dihydroxy-6-(3-hydroxypropoxy)-7-methoxy-2,8-bis(3-me-
1-Hydroxy-3,6-bis(2,3-epoxypropoxy)-7-methoxy-2,8-bis(3-me-
thylbut-2-enyl)-9H-xanthen-9-one (4): m. p. 156±157 8C; UV: thylbut-2-enyl)-9H-xanthen-9-one (10): m.p. 128±130 8C; UV:
lmax (log e) = 244 (4.53), 259 (4.47), 317 (4.41) nm; IR: lmax (log e) = 244 (4.50), 262 (4.54), 312 (4.39), 351 (3.85) nm;
-
1
1
±1
1
nmax = 3091 (b), 1645, 1596, 1465, 1434, 1292, 1206 cm ; H- IR(CHCl ): n
= 3389 (b), 1644, 1598, 1463, 1430 cm ; H-
3
max
NMR: d = 1.68 (6H, s, H-5¢, H-5¢¢), 1.77 (3H, s, H-4¢), 1.84 (3H, s, NMR: d = 1.68 (6H, s, H-5¢, H-5¢¢), 1.81 (3H, s, H-4¢), 1.84(3H, s,
H-4¢¢), 3.45 (2H, d, J = 7 Hz, H-1¢), 3.78 (3H, s, 7-OCH ), 4.11 H-4¢¢), 3.38 (2H, d, J = 7 Hz, H-1¢), 3.80 (1H, s, 7-OCH ), 4.13 (2H,
3
3
(
6
(
2H, d, J = 7 H, H-1¢¢), 5.24 (1H, bt, H-2¢), 5.30 (1H, bt, H-2¢¢), d, J = 7 Hz, H-1¢¢), 5.24 (2H, bt, H-2¢ and H-2¢¢), 6.28 (1H, s, H-4),
.25 (1H, s, H-4), 6.36 (1H, s, 3-OH), 6.73 (1H, s, H-5), 13.89 6.73 (s, H-5), 13.47 (s, 1-OH), substituent group 2OCH2-
1H, s, 1-OH), substituent group OCH CH CH OH: 4.24 (2H, t, CH(O)CH : 4.02 and 4.29 (1H, dd, J = 2, 11 Hz and 1H, dd,
2
2
2
2
J = 6 Hz, OCH ), 2.15 (2H, m, CH ), 3.92 (2H, q, CH O), 1.98 J = 3, 11 Hz, OCH ), 4.06 and 4.38 (1H, dd, J = 2, 11 Hz and 1H,
2
2
2
2
913
(
1H, bt, OH); MS: m/z = 468 (91), 425 (40), 413 (46), 397 dd, J = 3, 11 Hz, OCH ), 3.44 (2H, m, 2CH), 2.78 and 2.95 (1H,
2
(
100), 365 (47), 320 (20), 307 (30); anal. calcd. for C H O : C dd, J = 3, 4 Hz and 1H, dd, J = 4, 10 Hz, CH ), 2.82 and 2.95 (1H,
27
32
7
2
6
9.2, H 6.9; found: C 69.2, H 7.0.
dd, J = 3, 4 Hz and 1H, dd, J = 4, 10 Hz, CH ); MS: m/z = 522
2
(
100), 478 (84), 466 (76), 450 (84), 437 (29), 422 (34), 408
(24), 394 (40), 374 (14), 360(15), 323 (14); anal. calcd. for
A mixture of mangostin (5 g, 12 mmol), chloroacetamide (2.28 g, C H O : C 69.0, H 6.6; found: C 69.3, H 6.8.
Preparation of amide derivatives 8 and 9
3
0
34
8
2
4 mmol) and potassium carbonate in acetone was stirred at
room temperature for 24 h. The reaction mixture was worked 1,3-Dihydroxy-6-(2,3-epoxypropoxy)-7-methoxy-2,8-bis(3-me-
up as usual and the residue was chromatographed on silica gel. thylbut-2-enyl)-9H-xanthen-9-one (11): m.p. 148±149 8C; UV:
Elution with dichloromethane/methanol (50:1) and recrystalli- lmax (log e) = 244 (4.53), 259 (4.49), 315 (4.41) nm; IR:
±
1
1
zation in acetone gave 8 (yield: 0.8 g, 14%) and (9) (yield: 0.9 g, nmax = 3306 (b), 1644, 1596, 1465, 1431 cm ; H-NMR:
6%) as yellow solids. d = 1.68 (6H, s, H-5¢, H-5¢¢), 1.81 (3H, s, H-4¢), 1.82 (3H, s, H-
¢¢), 3.37 (2H, d, J = 7 Hz, H-1¢), 3.80 (3H, s, 7-OCH ), 4.08 (2H,
1
4
3
1
,6-Dihydroxy-3-(2-amino-2-oxoethoxy)-7-methoxy-2,8-bis(3-me-
thylbut-2-enyl)-9H-xanthen-9-one (8): m.p. 242±243 8C; UV: lmax 6.82 (1H, s, H-5), 13.41 (1H, s, 1-OH), substituent group OCH2-
log e) = 243 (4.49), 258 (4.46), 314 (4.36), 350 (3.81) nm; IR: CH(O)CH 4.03 and 4.31 (1H, dd, J = 2, 11 Hz and 1H, dd,
d, J = 7 Hz, H-1¢¢), 5.25 (2H, bt, H-2¢ and H-2¢¢), 6.29 (1H, s, H-4),
(
2
:
-1 1
nmax = 3473, 3349, 3267 (b), 1689, 1651, 1604,1574 cm ; H-NMR: J = 3, 11 Hz, OCH ), 3.41 (1H, m, CH), 2.80 and 2.94 (1H, dd,
2
d = 1.69 (6H, s, H-5¢, H-5¢¢), 1.80 (3H, s, H-4¢), 1.83 (3H, s, H-4¢¢), J = 3, 4 Hz and 1H, dd, J = 4, 10 Hz, CH ); MS: m/z = 466 (38),
2
3
.44 (2H, d, J = 7 Hz, H-1¢), 3.81 (3H, s, 7-OCH ), 4.10 (2H, d, J = 7 465 (80), 422 (58), 410 (72), 394 (100), 378 (23), 360 (23), 352
3
Hz, H-1¢¢), 5.23 (1H, bt, H-2¢), 5.27 (1H, bt, H-2¢¢), 6.31 (1H, s, H-4), (21), 339 (29), 322 (35); anal. calcd. for C H O : C 69.5, H 6.5;
27
30
7
6.44 (1H, s, 6-OH), 6.86 (1H, s, H-5), 13.58 (1H, s, 1-OH), substitu- found: C 69.8, H 6.8.
ent group OCH CONH : 4.59 (2H, s, OCH ), 5.57 and 6.59 (2H,
2
2
2
2
bs, NH ); MS: m/z = 467 (70), 424 (28), 412 (40), 409 (28), 396 Preparation of hydroxy amino derivatives 19 and 20
2
(
100), 367 (58), 329 (30); anal. calcd. for C H O N: C 66.8, H 6.3, Dimethylamine (0.5 mL) was added to a solution of epoxide deri-
26 29 7
N 3.0; found: C 66.7, H 6.4, N 3.0.
vative 11 or 10 (500 mgeach) in methanol (5 mL) and the reac-
tion mixtures were refluxed for 6 h. The solution was evaporated
to remove the solvent and excess amine. The residue was chro-
Mahabusarakam W et al.Prenylated Xanthones as¼ Planta Med 2006; 72: 912±916