Synthesis and Anti-tumor Evaluation of B-ring Modified Caged Xanthone Analogues
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6.02—6.15 (m, 1H, C12-H), 7.11 (dd, J=8.5, 0.9 Hz,
Yield 89%; white solid; m.p. 100—102 ℃; H NMR
1H, C3-H), 7.28—7.32 (m, 3H, C2-H, C3-H, C8-H); IR
(KBr) ν: 3414, 3061, 2917, 1640, 1614, 1481, 1439,
1290 cm-1; EI-MS m/z: 364 (M+). Anal. calcd for
C22H20O5: C 72.51, H 5.53; found C 72.12, H 5.44.
Caged xanthone (15b) Yield 7%; yellow solid;
m.p. 109—111 ℃; 1H NMR (Acetone-d6, 300 MHz) δ:
1.78—1.96 (m, 2H, C14-H), 2.22—2.53 (m, 2H, C17-H),
2.67—2.75 (m, 1H, C15-H), 3.46—3.51 (m, 3H, C7-H,
C11-H), 3.93 (d, J=7.6 Hz, 1H, C16-H), 4.50 (dd, J=7.6,
3.8 Hz, 1H, C16-H), 4.55—4.63 (m, 2H, C19-H), 4.94—
5.12 (m, 2H, C13-H), 5.14—5.21 (m, 1H, C18-H), 5.95—
6.08 (m, 1H, C12-H), 6.71 (d, J=8.7 Hz, 1H, C2-H),
7.22 (d, J=7.0 Hz, 1H, C8-H), 7.68 (d, J=8.7 Hz, 1H,
C1-H), 9.44 (s, 1H, C3-OH); IR (KBr) ν: 3412, 3076,
2982, 2924, 1744, 1701, 1638, 1608, 1435, 1285, 786
(CDCl3, 300 MHz) δ: 4.69—4.82 (m, 6H, 3×CH2CH=
CH2), 5.30—5.55 (m, 6H, 3×CH2CH=CH2), 6.08—
6.24 (m, 3H, 3×CH2CH=CH2), 7.18 (d, J=9.0 Hz, 1H,
ArH), 7.42 (dd, J=9.1, 3.1 Hz, 1H, ArH), 7.57 (d, J=
9.1 Hz, 1H, ArH), 7.62 (d, J=3.1 Hz, 1H, ArH), 7.94 (d,
J=9.0 Hz, 1H, ArH); IR (KBr) ν: 3414, 3083, 2917,
1657, 1617, 1594, 1488, 1446, 1313, 1213, 1080, 825,
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+
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776 cm ; EI-MS m/z: 364 (M ).
3,4,6-Tris(allyloxy)-9H-xanthen-9-one
(14b)
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Yield 91%; white solid; m.p. 77—78 ℃; H NMR
(CDCl3, 300 MHz) δ: 4.66—4.74 (m, 6H, 3×CH2CH=
CH2), 5.23—5.37 (m, 6H, 3×CH2CH=CH2), 6.05—
6.23 (m, 3H, 3×CH2CH=CH2), 6.95—6.99 (m, 3H,
ArH), 8.03 (d, J=9.0 Hz, 1H, ArH), 8.23 (d, J=9.0 Hz,
1H, ArH); IR (KBr) ν: 2917, 1650, 1622, 1600, 1437,
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1
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+
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1286, 1186, 1077, 844, 774, 685 cm ; EI-MS m/z: 364
cm ; EI-MS m/z: 364 (M ). Anal. calcd for C22H20O5:
C 72.51, H 5.53; found C 72.19, H 5.77.
(M+).
3,4,5-Tris(allyloxy)-9H-xanthen-9-one
(14c)
Caged xanthone (15c) Yield 6%; yellow solid;
m.p. 91—93 ℃; H NMR (Acetone-d6, 300 MHz) δ:
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Yield 87%; white solid; m.p. 113—114 ℃; H NMR
(CDCl3, 300 MHz) δ: 4.78—4.85 (m, 6H, 3×CH2CH=
CH2), 5.19—5.64 (m, 6H, 3×CH2CH=CH2), 6.12—
6.30 (m, 3H, 3×CH2CH=CH2), 7.22 (d, J=9.0 Hz, 1H,
ArH), 7.36 (t, J=8.0 Hz, 1H, ArH), 7.47 (dd, J=8.0,
1.6 Hz, 1H, ArH), 7.79 (dd, J=8.0, 1.6 Hz, 1H, ArH),
7.96 (d, J=9.0 Hz, 1H, ArH); IR (KBr) ν: 3415, 1658,
1.85—1.91 (m, 2H, C14-H), 2.47—2.70 (m, 3H, C15-H,
C17-H), 3.47—3.57 (m, 3H, C7-H, C11-H), 3.86 (d, J=
7.8 Hz, 1H, C16-H), 4.68 (q, J=7.8, 3.8 Hz, 1H, C16-H),
5.03—5.15 (m, 2H, C13-H), 5.20—5.27 (m, 1H, C18-H),
5.95—6.12 (m, 1H, C12-H), 6.90 (d, J=8.1 Hz, 1H,
C2-H), 7.30 (d, J=7.5 Hz, 1H, C8-H), 7.34 (d, J=8.1
Hz, 1H, C1-H), 8.08 (s, 1H, C4-OH); IR (KBr) ν: 3473,
3076, 2982, 2924, 1740, 1664, 1640, 1614, 1503, 1450,
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1615, 1601, 1489, 1441, 1290, 1088, 769, 739 cm ;
EI-MS m/z: 364 (M+).
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+
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1-Hydroxy-3,5,6-tris(allyloxy)-9H-xanthen-9-one
(14d) Yield 85%; yellow solid; m.p. 77—78 ℃; H
1318, 1258, 1124, 923 cm ; EI-MS m/z: 364 (M ).
Anal. calcd for C22H20O5: C 72.51, H 5.53; found C
72.38, H 5.49.
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NMR (CDCl3, 300 MHz) δ: 4.62—4.75 (m, 6H, 3×
CH2CH=CH2), 5.32—5.50 (m, 6H, 3×CH2CH=CH2),
6.03—6.17 (m, 3H, 3×CH2CH=CH2), 6.35 (d, J=2.0
Hz, 1H, ArH), 6.51 (d, J=2.0 Hz, 1H, ArH), 6.97 (d,
J=9.0 Hz, 1H, ArH), 7.95 (d, J=9.0 Hz, 1H, ArH),
12.89 (s, 1H, OH); IR (KBr) ν: 3473, 1658, 1604, 1569,
Caged xanthone (15d) Yield 6%; yellow solid;
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m.p. 54—55 ℃; H NMR (Acetone-d6, 300 MHz) δ:
1.89—1.91 (m, 2H, C14-H), 2.17—2.53 (m, 2H, C17-H),
2.67—2.72 (m, 1H, C15-H), 3.37—3.41 (m, 2H, C11-H),
3.50—3.53 (m, 1H, C7-H), 3.92 (d, J=3.7 Hz, 1H,
C16-H), 4.47 (dd, J=7.7, 3.7 Hz, 1H, C16-H), 4.67—
4.71 (m, 1H, C19-H), 4.91—4.95 (m, 1H, C19-H), 5.04—
5.12 (m, 2H, C13-H), 5.58—5.64 (m, 1H, C18-H), 5.93—
6.05 (m, 1H, C12-H), 6.07 (s, 1H, C2-H), 7.31 (d, J=6.8
Hz, 1H, C8-H), 9.83 (s, 1H, C3-OH), 12.50 (s, 1H,
C1-OH); IR (KBr) ν: 3449, 2922, 1748, 1634, 1600,
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1516, 1443, 1299, 1166, 814, 690 cm ; EI-MS m/z:
380 (M+).
General procedure for the synthesis of caged xan-
thones (15a—15e)
A stirred solution of tri(allyloxy)-9H-xanthen-9-one
(10a—10d, 0.82 mmol) in decalin (10 mL) was refluxed
under N2 protection for 3 h, then cooled to 25 ℃ and
100 mL of petroleum ether was added. The precipitate
was filtrated and washed with petroleum. The crude
residue was purified by chromatography on a silica-gel
column eluted with PE-EtOAc (V∶V=10∶1) and then
crystallized from methanol-H2O (V∶V=5∶1) to af-
ford caged xanthones 15a—15e.
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1582, 1500, 1430, 1271, 1131 cm ; EI-MS m/z: 380
(M+). Anal. calcd for C22H20O6 : C 69.46, H 5.30; found
C 69.52, H 5.30.
Caged xanthone (15e) Yield 10%; yellow solid;
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m.p. 55—57 ℃; H NMR (Acetone-d6, 300 MHz) δ:
1.78—1.91 (m, 2H, C14-H), 2.37—2.65 (m, 2H, C17-H),
2.68—2.73 (m, 1H, C15-H), 3.26—3.30 (m, 2H, C11-H),
3.45—3.49 (m, 1H, C7-H), 3.85 (d, J=7.8 Hz, 1H,
C16-H), 4.35 (dd, J=7.8, 3.8 Hz, 1H, C16-H), 4.60—
4.69 (m, 2H, C19-H), 4.85—4.99 (m, 2H, C13-H), 5.18—
5.24 (m, 1H, C18-H), 5.83—5.96 (m, 1H, C12-H), 6.14 (s,
1H, C4-H), 7.30 (d, J=7.0 Hz, 1H, C8-H), 9.77 (s, 1H,
C3-OH), 12.83 (s, 1H, C1-OH); IR (KBr) ν: 3447, 3220,
Caged xanthone (15a) Yield 8%; yellow solid;
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m.p. 85—86 ℃; H NMR (Acetone-d6, 300 MHz) δ:
1.79—1.94 (m, 2H, C14-H), 2.43—2.65 (m, 1H, C17-H),
2.67—2.76 (m, 2H, C15-H, C17-H), 3.48—3.52 (m, 1H,
C7-H), 3.90 (d, J=7.8 Hz, 1H, C16-H), 4.44 (q, J=7.8,
3.9 Hz, 1H, C16-H), 4.52—4.64 (m, 4H, C11-H, C19-H),
5.10—5.22 (m, 1H, C18-H), 5.24—5.47 (m, 2H, C13-H),
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1740, 1642, 1621, 1582, 1571, 1450, 1328, 1118 cm ;
380 (M+). Anal. calcd for C22H20O6 : C 69.46, H 5.30;
Chin. J. Chem. 2012, 30, 35—42
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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