4290
S. Vogel et al. / Bioorg. Med. Chem. 16 (2008) 4286–4293
4.2.4. 2,20,40-Trihydroxy-60-methoxy-30-prenylchalcone
(6). Yield 40%; Orange-yellow amorphous powder; mp
84–85 ꢁC; UV kmax 365.0 nm; EI-MS (pos. mode) m/z:
354 [M]+ (42), 293 (100), 179 (85); EI-HRMS (pos.
mode) m/z: 354.1459 (calcd for C21H22O5, 354.1467);
1H NMR (CDCl3) d (ppm): 1.78 (3H, s, H3-500), 1.83
(3H, s, H3-400), 3.41 (2H, d, J = 7.4, H2-100), 3.89 (3H,
s, OCH3), 5.30 (1H, t, J = 7.4, H-200), 5.60 (1H, s,
OH), 5.94 (1H, s, OH), 6.23 (1H, s, H-50), 6.85 (1H,
m, H-5), 6.96 (1H, d, J = 15.9, H-b), 6.98 (1H, m, H-
3), 7.25 (1H, m, H-4), 7.55 (1H, dd, J = 8.0, 1.6, H-6),
8.04 (1H, d, J = 15.9, H-a), 14.56 (1H, s, OH-20); 13C
NMR (acetone-d6) d (ppm): 193.8 (CO), 166.4 (C-20),
162.9 (C-40), 162.0 (C-60), 157.7 (C-2), 138.3 (C-b),
132.2 (C-4), 131.0 (C-300), 129.6 (C-6), 128.3 (C-a),
124.0 (C-200), 123.5 (C-1), 120.9 (C-5), 117.1 (C-3),
108.9 (C-30), 106.4 (C-10), 91.7 (C-50), 56.1 (OCH3),
25.9 (C-500), 22.1 (C-100), 17.9 (C-400).
(22), 179 (100); EI-HRMS (pos. mode) m/z: 370.1416
(calcd for C21H22O6, 370.1416); 1H NMR (CDCl3) d
(ppm): 1.78 (3H, s, H3-500), 1.83 (3H, s, H3-400), 3.40
(2H, d, J = 7.4, H2-100), 3.90 (3H, s, OCH3), 5.05 (1H,
s, OH), 5.29 (1H, t, J = 7.4, H-200), 5.94 (1H, s, OH),
6.24 (1H, s, H-50), 6.39 (1H, t, J = 2.1, H-4), 6.65 (2H,
d, J = 2.1, H-2 and H-6), 7.60 (1H, d, J = 15.6, H-b),
7.80 (1H, d, J = 15.6, H-a), 14.50 (1H, s, OH-20); 13C
NMR (acetone-d6) d (ppm): 193.3 (CO), 166.4 (C-20),
163.1 (C-40), 162.0 (C-60), 159.9 (C-3 and C-5), 142.9
(C-b), 138.5 (C-1), 131.1 (C-300), 128.6 (C-a), 123.9 (C-
200), 109.0 (C-30), 107.6 (C-2 and C-6), 106.3 (C-10),
105.6 (C-4), 91.8 (C-50), 56.2 (OCH3), 25.9 (C-500), 22.1
(C-100), 17.9 (C-400).
4.2.8. 20,3,4,40,5-Pentahydroxy-60-methoxy-30-prenyl-
chalcone (10). Yield 69%; Orange amorphous powder;
mp 64–66 ꢁC; UV kmax 385.0 nm; EI-MS (pos. mode)
m/z: 386 [M]+(32), 371 [MꢀCH3]+ (4), 343 [M-C3H7]+
(8), 179 (100), 153 (68); EI-HRMS (pos. mode) m/z:
386.1360 (calcd for C21H22O7 386.1366); 1H NMR
(DMSO-d6) d (ppm): 1.61 (3H, s, H3-500), 1.70 (3H, s,
H3-400), 3.14 (2H, d, J = 7.0, H2-100), 3.88 (3H, s,
OCH3), 5.13 (1H, t, J = 7.0, H-200), 6.08 (1H, s, H-50),
6.65 (2H, s, H-2 and H-6), 7.49 (1H, d, J = 15.4, H-b),
7.66 (1H, d, J = 15.4, H-a), 14.70 (1H, s, OH-20); 13C
NMR (acetone-d6) d (ppm): 193.2 (CO), 166.4 (C-20),
162.8 (C-40), 161.9 (C-60), 146.8 (C-3 and C-5), 143.9
(C-b), 136.7 (C-4), 130.9 (C-300), 127.8 (C-1), 125.7 (C-
a), 124.0 (C-200), 108.9 (C-30), 108.8 (C-2 and C-6),
106.3 (C-10), 91.7 (C-50), 56.2 (OCH3), 25.9 (C-500),
22.1 (C-100), 17.9 (C-400).
4.2.5. 20,3,40-Trihydroxy-60-methoxy-30-prenylchalcone
(7). Yield 55%; Orange amorphous powder; mp 79–
80 ꢁC; UV kmax 355.0 nm; EI-MS (pos. mode) m/z: 354
[M]+ (64), 339 [MꢀCH3]+ (12), 311 [M-C3H7]+ (40),
179 (100); EI-HRMS m/z: 354.1465 (calcd for
1
C21H22O5, 354.1467); H NMR (CDCl3) d (ppm): 1.78
(3H, s, H3-500), 1.83 (3H, s, H3-400), 3.41 (2H, d,
J = 7.4, H2-100), 3.90 (3H, s, OCH3), 4.99 (1H, s, OH),
5.29 (1H, t, J = 7.4, H-200), 5.95 (1H, s, OH), 6.23 (1H,
s, H-50), 6.86 (1H, ddd, J = 8.0, 2.7, 1.1, H-4), 7.07
(1H, m, H-2), 7.18 (1H, m, H-6), 7.27 (1H, t, J = 8.0,
H-5), 7.70 (1H, d, J = 15.6, H-b), 7.85 (1H, d,
J = 15.6, H-a), 14.52 (1H, s, OH-20); 13C NMR (ace-
tone-d6) d (ppm): 193.3 (CO), 166.4 (C-20), 163.2 (C-
40), 162.1 (C-60), 158.8 (C-3), 142.6 (C-b), 137.9 (C-1),
131.1 (C-300), 130.9 (C-5), 128.7 (C-a), 123.9 (C-200),
120.9 (C-6), 118.2 (C-4), 115.3 (C-2), 108.9 (C-30),
106.3 (C-10), 91.8 (C-50), 56.2 (OCH3), 25.9 (C-500),
22.1 (C-100), 17.9 (C-400).
4.2.9. 20,40-Dihydroxy-3,4,60-trimethoxy-30-prenylchal-
cone (11). Yield 78%; Orange amorphous powder; mp
154–155 ꢁC; UV kmax 375.1 nm; EI-MS (pos. mode) m/
z: 398 [M]+ (80), 355 [M-C3H7]+ (53), 179 (100); ESI-
HRMS (pos. mode) m/z: 398.1726 (calcd for
C23H26O6, 398.1729); 1H NMR (DMSO-d6) d (ppm):
1.61 (3H, s, H3-500), 1.70 (3H, s, H3-400), 3.14 (2H, d,
J = 6.6, H2-100), 3.81 (3H, s, OCH3), 3.83 (3H, s,
OCH3), 3.87 (3H, s, OCH3), 5.14 (1H, t, J = 6.6, H-
200), 6.09 (1H, s, H-50), 7.03 (1H, d, J = 8.5, H-5), 7.26
(1H, dd, J = 1.6, 8.5, H-6) 7.32 (1H, J = 1.6, H-2),
7.68 (1H, d, J = 15.6, H-b), 7.83 (1H, d, J = 15.6, H-
a), 14.57 (1H, s, OH-20); 13C NMR (CDCl3) d (ppm):
193.2 (CO), 166.4 (C-20), 162.9 (C-40), 162.0 (C-60),
152.6 (C-4), 150.6 (C-3), 143.1 (C-b), 131.0 (C-300),
129.4 (C-1), 126.4 (C-a), 124.0 (C-200), 123.6 (C-6),
112.6 (C-5), 111.6 (C-2), 108.9 (C-30), 106.3 (C-10),
91.7 (C-50), 56.2 (3· OCH3-3,4,60), 25.9 (C-500), 22.1
(C-100), 17.9 (C-400).
4.2.6. 20,3,4,40-Tetrahydroxy-60-methoxy-30-prenylchal-
cone (3-hydroxyxanthohumol, 8). Yield 42%; Orange
amorphous powder; mp 127 ꢁC; UV kmax 380.0 nm;
EI-MS (pos. mode) 370 [M]+ (57), 355 [MꢀCH3]+ (9),
327 (31), 179 (100); EI-HRMS (pos. mode) m/z:
370.1416 (calcd for C21H22O6, 370.1416); 1H NMR
(CDCl3) d (ppm): 1.77 (3H, s, H3-500), 1.83 (3H, s, H3-
400), 3.40 (2H, d, J = 7.1, H2-100), 3.90 (3H, s, OCH3),
5.29 (1H, t, J = 7.1, H-200), 5.72 (1H, s, OH), 5.94 (1H,
s, H-50), 6.25 (1H, s, OH), 6.87 (1H, s, OH), 7.08 (1H,
d, J = 8.2, H-5), 7.09 (1H, dd, J = 8.2, 1.9, H-6) 7.15
(1H, J = 1.9, H-2), 7.68 (1H, d, J = 15.6, H-b), 7.76
(1H, d, J = 15.6, H-a), 14.65 (1H, s, OH-20); 13C
NMR (acetone-d6) d (ppm): 193.3 (CO), 166.4 (C-20),
162.8 (C-40), 161.9 (C-60), 148.8 (C-4), 146.4 (C-3),
143.5 (C-b), 131.0 (C-300), 128.8 (C-1), 125.6 (C-a),
124.0 (C-200), 123.1 (C-6), 116.5 (C-5), 115.3 (C-2),
108.9 (C-30), 106.3 (C-10), 91.7 (C-50), 56.2 (OCH3),
25.9 (C-500), 22.1 (C-100), 17.9 (C-400).
4.2.10. 20,4,40-Trihydroxy-60-methoxy-chalcone (Heli-
chrysetin, 12). Yield 76%; Orange-yellow amorphous
powder; mp 253–254 ꢁC; UV kmax 365.0 nm; EI-MS
(pos. mode) m/z: 286 [M]+ (89), 285 [MꢀH]+ (80), 167
(100); 1H NMR (DMSO-d6) d (ppm): 3.87 (3H, s,
OCH3), 5.91 (1H, d, J = 2.2, H-30), 6.01 (1H, d,
J = 2.2, H-50), 6.84 (2H, d, J = 8.8, H-3 and H-5), 7.57
(2H, J = 8.8, H-2 and H-6), 7.62 (1H, d, J = 15.6, H-
b), 7.69 (1H, d, J = 15.6, H-a), 13.96 (1H, s, OH-20);
13C NMR (acetone-d6) d (ppm): 193.2 (CO), 169.1 (C-
4.2.7. 20,3,40,5-Tetrahydroxy-60-methoxy-30-prenylchal-
cone (9). Yield 71%; Orange amorphous powder; mp
141–142 ꢁC; UV kmax 355.0 nm; EI-MS (pos. mode)
370 [M]+ (73), 355 [MꢀCH3]+ (11), 327 [M-C3H7]+