170 Y.Wang et al.
MS m/z: 371 [MϩNa]ϩ, 387 [MϩK]ϩ; and
Yield: 8.1%.
0.93 (3H, s, H-18), 1.01 (3H, s, H-19), 1.97 (3H,
s, H-21); MS m/z: 385 [MϩNa]ϩ, 401 [MϩK]ϩ;
andYield: 22.6%.
3β, 11α-dihydroxy-16α, 17α-epoxy-pregn-5-
en-7, 20-dione (16), mp: 280.5–282.1°C; IR (KBr)
νmax (cmϪ1): 3528, 3409, 2966, 2941, 1703, 1459,
1377, 1361, 1299, 1078, 1059; 1H NMR (DMSO-
d6) δ (ppm): 3.38 (m, H-3), 5.65 (s, H-6), 3.98 (m,
H-11), 3.93 (t, Jϭ4.8 Hz, H-16), 0.95 (3H, s,
H-18), 1.25 (3H, s, H-19), 1.97 (3H, s, H-21); MS
m/z: 383 [MϩNa]ϩ, 399 [MϩK]ϩ; and Yield:
8.3%.
Transformation of 3b-hydroxy-pregn-5, 16
(17)-dien-20-one (3)
Elution with ethyl acetate/petroleum ether (3:1) gave
four metabolites.
3β, 7α-dihydroxy-pregn-5, 16 (17)-dien-20-one
(11), mp: 112.1–112.8°C; IR (KBr) νmax (cmϪ1):
3480, 3415, 3366, 3309, 2934, 1660, 1588, 1460,
1432, 1372, 1233, 1055, 1019; 1H NMR (DMSO-
d6) δ (ppm): 3.32 (m, H-3), 5.43 (d, Jϭ4.8 Hz,
H-6), 3.69 (m, H-7), 6.90 (m, H-16), 0.82 (3H, s,
H-18), 0.93 (3H, s, H-19), 2.21 (s, H-21); MS m/z:
353 [MϩNa]ϩ, 369 [MϩK]ϩ; andYield: 17.6%.
3β, 7α, 11α-trihydroxy-pregn-5, 16-dien-20-one
(12), mp: 274.3–275.6°C; IR (KBr) νmax (cmϪ1):
3493, 3368, 2973, 2936, 2874, 1646, 1457, 1436,
The 13C NMR signals of the compounds are
presented in Table I.
Table I. 13C NMR signals for the substrates and the metabolites
of 3β-hydroxy-5-ene steroids (δ ppm).
C
1
5
6
7
2
8
9
10
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
37.2 35.4 36.7 36.5 37.3 37.0 38.4 29.0
31.5 31.4 31.4 31.6 31.6 31.6 31.6 31.3
71.4 69.9 69.9 69.9 71.7 71.3 70.2 69.3
42.2 42.2 42.2 41.8 42.3 42.2 42.8 42.3
141.3 144.0 143.8 141.4 140.9 146.3 144.6 141.2
120.8 124.4 124.6 127.3 121.4 123.7 124.3 123.5
31.5 62.6 63.1 71.8 31.8 65.2 63.5 64.4
31.5 37.1 37.6 39.9 31.9 37.4 37.1 38.5
50.3 41.9 41.8 48.3 50.1 41.9 47.8 74.7
36.7 37.1 36.9 36.2 36.6 37.4 38.5 42.4
20.4 19.8 20.1 20.5 21.1 20.7 67.2 26.4
30.8 31.2 36.3 36.8 38.9 38.2 49.1 34.0
47.5 46.6 42.0 42.8 44.0 43.8 43.6 43.4
51.8 44.7 43.8 50.8 57.0 49.7 49.5 45.0
21.8 21.5 23.0 30.2 24.5 24.4 23.7 23.7
35.8 36.7 30.0 25.7 22.9 22.9 22.6 22.4
221.3 220.2 80.3 80.0 63.8 63.5 62.8 62.6
13.2 13.1 11.1 11.4 13.2 13.0 14.1 12.3
19.4 18.1 18.0 18.9 19.4 18.2 17.7 21.4
1
1376, 1051, 1024; H NMR (DMSO-d6) δ (ppm):
3.30 (m, H-3), 5.45 (d, Jϭ5.2 Hz, H-6), 3.67 (dd,
Jϭ5.6, 8.8 Hz, H-7), 1.36 (H-9), 3.93 (m, H-11),
1.16 (H-12), 2.52 (H-12), 6.90 (t, Jϭ1.2 Hz, H-16),
0.80 (3H, s, H-18), 1.03 (3H, s, H-19), 2.21 (3H,
s, H-21); MS m/z: 369 [MϩNa]ϩ, 385 [MϩK]ϩ;
andYield: 8.9%.
3β, 7α, 9α-trihydroxy-pregn-5, 16-dien-20-one
(13), mp: 261.4–263.1°C; IR (KBr) νmax (cmϪ1):
3347, 2938, 1662, 1648, 1457, 1437, 1373, 1053,
1
1019; H NMR (DMSO-d6) δ (ppm): 3.28 (m,
H-3), 5.48 (dd, Jϭ1.2, 4.8 Hz, H-6), 3.82 (br. s,
H-7), 6.93 (t, Jϭ1.2 Hz, H-16), 0.84 (3H, s, H-18),
1.02 (3H, s, H-19), 2.23 (3H, s, H-21); MS m/z: 369
[MϩNa]ϩ, 385 [MϩK]ϩ; andYield: 15.4%.
3β, 14α-dihydroxy-pregn-5, 16-dien-7, 20-dione
–
–
–
–
–
–
–
–
209.4 209.6 208.7 208.7
31.5 31.3 31.3 31.4
(14), mp: 196.3–197.8°C; IR (KBr) ν
(cmϪ1):
max
C
3
11
12
13
14
4
15
16
3361, 3230, 2946, 2755, 1750, 1640, 1619, 1467,
1
1371, 1275, 1202, 1024; H NMR (DMSO-d6) δ
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
36.7 36.3 38.1 28.9 36.0 37.1 38.1 38.0
29.6 31.2 31.5 31.2 31.2 31.5 31.5 31.3
69.9 69.6 70.0 69.2 69.0 71.6 70.0 69.6
42.1 42.0 42.8 42.3 41.9 42.2 42.8 42.4
141.6 143.9 144.8 141.4 168.2 141.1 144.7 167.2
120.0 124.2 124.0 123.5 125.6 120.9 124.0 124.1
31.3 63.4 63.6 64.7 199.2 31.3 63.1 200.4
30.9 35.4 35.6 37.0 46.9 29.7 35.0 38.9
49.9 41.5 48.3 75.2 43.2 50.3 48.3 55.2
36.2 36.8 38.5 42.5 37.9 36.6 40.9 40.2
20.1 19.8 67.0 26.5 19.3 30.4 66.9 66.6
34.3 34.1 45.6 30.6 25.4 31.4 42.3 41.9
45.4 45.2 45.7 45.8 52.1 41.5 38.6 41.6
55.8 49.5 49.7 45.1 80.7 45.5 39.0 42.2
31.7 31.7 31.5 31.6 43.0 27.5 26.4 28.7
145.1 145.7 146.0 146.0 144.4 60.5 60.8 60.9
154.2 154.2 154.2 154.4 150.6 71.0 70.2 69.3
15.5 15.4 16.8 15.0 20.3 15.1 15.9 16.0
18.9 17.7 17.7 21.4 17.0 19.3 17.7 16.8
196.3 196.1 196.2 196.3 196.6 204.9 205.0 205.0
26.9 26.9 27.1 27.1 27.2 25.9 25.9 25.9
(ppm): 3.41 (m, H-3), 5.62 (d, Jϭ2.0 Hz, H-6),
6.83 (t, Jϭ1.6 Hz, H-16), 0.93 (3H, s, H-18), 1.13
(3H, s, H-19), 2.22 (3H, s, H-21); MS m/z: 367
[MϩNa]ϩ, 383 [MϩK]ϩ; andYield: 13.2%.
Transformation of 16a, 17a -epoxy-3b-hydroxy-
pregn-5-en-20-one (4)
Elution with ethyl acetate/petroleum ether (1:1) gave
two metabolites.
3β, 7α, 11α-trihydroxy-16α, 17α-epoxy-pregn-5-
en-20-one (15), mp: 251.2–253.7°C; IR (KBr) νmax
(cmϪ1): 3484, 3292, 2973, 2934, 2891, 1693, 1458,
1
1437, 1419, 1375, 1362, 1062, 1044; H NMR
(DMSO-d6) δ (ppm): 3.30 (m, H-3), 5.43 (d, Jϭ5.6
Hz, H-6), 3.55 (br. s, H-7), 1.29 (H-9), 3.87 (m,
H-11), 1.18 (H-12), 2.14 (H-12), 3.94 (s, H-16),