866
J.-L. Yan / Steroids 65 (2000) 863–870
12: mp 210–213°C; [␣]D25-63 (c 0.5, CHCl3); IR (KBr)
1.15 (3 H, s, 19-CH3); 13C NMR (CDCl3): ␦ 217.9 (s, C-17),
208.4 (s, C-3), 196.9 (s, C-7), 159.5 (s, C-14), 126.6 (s,
C-8), 50.8 (s, C-13), 47.8 (t, C-4), 44.1 (d, C-9), 37.9 (t,
C-2), 36.2 (s, C-5), 35.7 (t, C-16), 34.9 (t, C-1), 33.7 (s,
C-10), 33.4 (d, C-6), 28.1 (t, C-12), 27.0 (t, C-15), 25.4 (q,
C-18), 19.9 (t, C-11), 17.4 (t, C-20), 16.2 (q, C-19); Crystal
data: monoclinic P 21, a ϭ 11.4169 (14) Å, b ϭ 11.9152
(21) Å, c ϭ 12.3751 (18) Å, Z ϭ 4. Intensity data were
collected on a CAD-4 diffractometer with /2 scan mode,
using monochromated MoK␣ radiation. Data were mea-
sured up to 2 of 55.0o. A total of 4230 reflections were
collected. Among them, 2618 were considered to be ob-
served ( Ͼ 2.08 (I)). Final agreement indices are Rf ϭ
0.038, Rw ϭ 0.039, GoF ϭ 1.52, based on anisotropic
refinement of all non-hydrogen atoms.; EIMS m/z [M]ϩ 312
(100), 297 (2), 284 (8), 267 (5), 255 (3), 241 (4), 227 (2),
213 (6), 199 (5), 188 (6), 173 (5), 161 (20), 148 (26), 133
(8), 115 (8), 105 (16); HREIMS m/z [M]ϩ 312.1726 (calcd.
for C20H24O3, 312.1725).
max 2925, 2850, 1735, 1705, 1450, 1410, 1375, 1340,
1280, 1240, 1210, 1170, 1100, 1055, 1030, and 1015 cmϪ1;
1H-NMR ␦ (CDCl3) 5.68 (1 H, ddd, J ϭ 2.6, 2.6, 5.2 Hz),
3.13 (1 H, d, J ϭ 15.1 Hz) and 1.44 (1 H, dd, J ϭ 2.1, 15.1
Hz) (H-4’s), 2.47 (1 H, dd,. J ϭ 8.8, 19.1 Hz) and 2.12 (1
H, m) (H-16’s), 2.10 (1 H, m, H-14), 1.90 (1 H, ddd, J ϭ
2.8, 4.5, 13.2 Hz) and 1.35 (1 H, ddd, J ϭ 6.8, 11.2, 12.8
Hz) (H-12’s), 1.79 (1 H, br d, J ϭ 9.7 Hz, H-9), 1.25 (3 H,
s, H-19), 1.17 (1 H, ddd, J ϭ 4.0, 5.1, 8.0 Hz, H-6), 0.79 (1
H, ddd, 2.1, 4.0, 4.3 Hz) and 0.57 (1 H, dd, J ϭ 4.3, 8.0 Hz)
(H-20’s), 0.75 (3 H, s, H-18); 13C-NMR ␦ (CDCl3) 220.5 (s,
C-17), 210.3 (s, C-3), 132.7 (s, C-8), 122.2 (d, C-7), 49.6 (d,
C-14), 49.0 (t, C-4), 47.2 (s, C-13), 41.8 (d, C-9), 38.5 (t,
C-2), 36.2 (t, C-1), 35.7 (t, C-16), 32.7 (s, C-10), 31.1 (t,
C-12), 31.0 (s, C-5), 21.1 (t, C-11), 21.0 (t, C-15), 19.1 (t,
C-20), 17.6 (d, C-6), 16.3 (q, C-19), 13.3 (q, C-18); HRE-
IMS m/z [M]ϩ 298.1941 (calcd for C20H26O2 298.1932);
EIMS m/z [M]ϩ 298 (100), 283 (15), 270 (8), 241 (16), 227
(11), 215 (18), 202 (15), 183 (11), 175 (13), 173 (23), 159
(14), 149 (33), 145 (14), 131 (19), 117 (13), 105 (27).
13: mp 178–180°C; [␣]D25-154 (c 0.5, CHCl3); IR (KBr)
max 3460 (OH), 2940, 2855, 1725, 1450, 1380, 1360,
1310, 1290, 1240, 1165 and 1070 cmϪ1; 1H-NMR ␦
(CDCl3) 5.64 (1 H, dt, J ϭ 5.0, 2.5 Hz, H-7), 3.75 (1 H, tt,
J ϭ 4.8, 11.2 Hz, H-3), 2.45 (1 H, dd, J ϭ 8.6, 14.9 Hz) and
2.11 (1 H, m) (H-16’s), 2.13 (1 H, m) and 0.93 (1 H, ddd,
J ϭ 2.1, 4.7, 12.5 Hz) (H-4’s), 1.12 (1 H, ddd, J ϭ 3.4, 5.0,
7.8 Hz, H-6), 1.04 (3 H, s, H-19), 0.76 (1 H, br dd J ϭ 3.4,
3.9 Hz) and 0.50 (1 H, dd, J ϭ 3.9, 7.8 Hz) (H-20’s), 0.75
(3 H, s, H-18); 13C-NMR ␦ (CDCl3) 220.5 (s, C-17), 69.7
(d, C-3), 132.6 (s, C-8), 122.6 (d, C-7), 49.5 (d, C-14), 42.5
(t, C-4), 47.2 (s, C-13), 41.9 (d, C-9), 31.9 (t, C-2), 34.7 (t,
C-1), 35.7 (t, C-16), 32.4 (s, C-10), 31.0 (t, C-12), 29.4 (s,
C-5), 20.9 (t, C-11), 20.7 (t, C-15), 19.5 (t, C-20), 17.9 (d,
C-6), 16.7 (q, C-19), 13.2 (q, C-18); HREIMS m/z [M]ϩ
300.2092 (calcd for C20H28O2 300.2089); EIMS m/z [M]ϩ
300 (100), 282 (22), 267 (27), 254 (9), 239 (16), 225 (14),
215 (69), 202 (27), 183 (22), 173 (31), 159 (35), 157 (50),
145 (40), 131 (47), 119 (31), 105 (72).
25
15: mp 208–210°C; [␣]D ϩ196 (c 0.3, CHCl3); IR
(KBr) max 3125, 1790, 1760, 1700, 1680, 1635, 1495,
1435, 1400, 1320, 1305, 1280, 1260, 1225, 1180, 1125,
1090, 1075 cmϪ1; UV(MeOH)
(log ⑀) 245 nm (4.04);
max
1H NMR (CDCl3): ␦ 3.12 (1 H, d, J ϭ 15.3 Hz, H-4) and
1.62 (1 H, dd, J ϭ 15.3, 1.8 Hz, H-4␣), 2.50–2.47 (3 H, m,
H-2 and H-16), 2.40–2.32 (5 H, m, H-14␣, H-11 and
H-15), 2.14–2.08 (2 H, m, H-1 and H-2␣), 1.91–1.83 (3 H,
m, H-6, H-1␣ and H-12), 1.51 (1 H, m, H-12␣), 1.42 (3
H, s, 19-CH3), 1.01 (2 H, d, J ϭ 6.6 Hz, H-20), 0.79 (3 H,
s, 18-CH3); 13C NMR (CDCl3): ␦ 219.3 (s, C-17), 207.5 (s,
C-3), 197.3 (s, C-7), 155.1 (s, C-9), 127.8 (s, C-8), 47.1 (s,
C-13), 46.5 (t, C-4), 44.5 (d, C-14), 39.1 (s, C-10), 37.4 (t,
C-16), 37.0 (t, C-2), 33.2 (d, C-6), 32.5 (t, C-1), 30.5 (s,
C-5), 28.3 (t, C-12), 24.6 (t, C-11), 23.6 (q, C-19), 22.9 (t,
C-15), 21.8 (t, C-20), 13.3 (q, C-18); EIMS m/z [M]ϩ 312
(100), 297 (10), 284 (11), 269 (18), 256 (17), 241 (11), 227
(25), 213 15), 199 (10), 185 (10), 171 (9), 157 (8), 141 (8),
128 (10), 115 (10), 105 (8); HREIMS m/z [M]ϩ 312.1728
(calcd. for C20H24O3, 312.1725)
25
14: mp 188–189°C; [␣]D ϩ195 (c 0.5, CHCl3); IR
Additional data of 16: mp 197–198°C (lit. 194–204°C
(KBr) max 3130, 3100, 3030, 1790, 1770, 1760, 1720,
[14]); [␣]D25 ϩ273 (c 0.15, CHCl3); IR (KBr): 3100, 3020,
1705, 1645, 1490, 1410, 1340, 1310, 1290, 1250, 1200,
1790, 1715, 1700, 1640, 1490, 1400, 1290, 1245, 1065,
1170, 1095, 1065,1020 cmϪ1; UV (MeOH)
(log ⑀)
max
1
1040 cmϪ1; UV (MeOH)
(log ⑀) 257 nm (4.28); H
1
max
257.5 nm (3.87); H NMR (CDCl3): ␦ 3.48 (1 H, ddd, J ϭ
1.8, 10.4, 18.5 Hz, H-15) and 2.97 (1 H, dddd, J ϭ 3.8,
3.8, 11.4, 18.5 Hz, H-15␣), 3.13 (1 H, d, J ϭ 15.0 Hz,
H-4) and 1.54 (1 H, dd, 1.8, 15.0 Hz, H-4␣), 2.71 (1 H,
ddd, J ϭ 3.2, 11.3, 19.6 Hz, H-16) and 2.19 (1 H, ddd, J ϭ
2.0, 10.8, 19.6 Hz, H-16␣), 2.50 (2 H, m, H-2), 2.25 (1 H,
dd, J ϭ 3.0, 11.0 Hz, H-9␣), 2.06 (1 H, ddd, J ϭ 2.2, 6.5,
13.1 Hz, H-1), 1.87 (1 H, ddd, J ϭ 3.2, 3.2, 13.1 Hz,
H-12) and 1.47 (1 H, dd, J ϭ 3.2, 13.1 Hz, H-12␣),
1.79–1.75 (2 H, m, H-6 and H-11), 1.68–1.57 (2 H, m,
H-1␣ and H-11␣), 1.66 (1 H, dd, J ϭ 5.3, 11.0 Hz) and 0.88
(1 H, dd, J ϭ 5.3, 8.8 Hz) (H-20’s), 1.20 (3 H, s, 18-CH3),
NMR (CDCl3): ␦ 5.94 (1 H, s, H-4), 2.51 (1 H, ddd, J ϭ 5.6,
5.6, 13.5 Hz, H-16) and 2.08 (1 H, m, H-16␣), 2.44 (1 H,
m, H-2) and 2.37 (1 H, dd, J ϭ 4.2, 17.4 Hz, H-2␣),
2.17–2.12 (2 H, m, H-8 and H-12), 2.04 (1 H, m, H-15),
1.91–1.85 (2 H, m, H-1 and H-12␣), 1.79 (1 H, ddd, J ϭ
3.8, 13.6, 16.4 Hz, H-6), 1.72–1.53 (2 H, m, H-15␣ and
H-1␣), 1.42–1.33 (2 H, m, H-7 and H-14␣), 1.28 (1 H, m,
H-11) and 0.86 (1 H, m, H-11␣), 1.14 (3 H, s, 19-CH3),
0.93 (3 H, s, 18-CH3), 0.88 (1 H, dd, J ϭ 4.8, 9.3 Hz) and
0.48 (1 H, dd, J ϭ 4.8, 9.8 Hz) (H-20’s), 0.79 (1 H, ddd, J ϭ
3.6, 3.6, 15.1 Hz, H-9␣); 13C NMR (CDCl3): ␦ 220.1 (s,