Pregnenes
1101
out, rinsed with 5% sodium hydrogen carbonate and water, and dried in air to obtain 550 mg of
product. Additional 30 mg was reclaimed from the filtrate by extraction with ether. The combined
products were chromatographed on a silica gel column (20 g).
2
1-Acetoxy-16β-azido-17α-hydroxypregn-4-ene-3,20-dione (3). Elution with a benzene–ether 3 : 1
mixture gave 450 mg (41%) of substance 3, m.p. 182–184 °C, [α] +24° (c 0.53). Mass spectrum,
D
+
m/z (%): 429 (M , C H N O ; 0.1), 401 (0.6), 387 (0.8), 341 (3.8), 326 (1.8), 325 (0.9), 324 (0.8),
2
3
31
3
5
3
1
6
13 (2.1), 300 (28.2), 271 (14.1), 243 (15.5), 231 (20.4), 229 (8.5), 211 (4.9), 197 (3.5), 187 (5.6),
73 (5.6), 159 (5.7), 147 (9.2), 131 (11.3), 121 (14.1), 107 (19.7), 105 (19.7), 91 (18.3), 79 (19.7),
7 (13.4), 55 (15.5), 43 (100), 41 (18.3). IR spectrum: 3 450 (OH); 2 950, 2 864 (CH); 2 104 (N ); 1 745
3
(
1
2
CO, acetate); 1 732 (CO-20); 1 702 (N ); 1 661 (CO-3); 1 615 (C=C); 1 234 (O–CO, acetate);
072 (C–O); 1 048 (C–O, acetate). H NMR spectrum: 1.04 s, 3 H (3 × H-18); 1.20 s, 3 H (3 × H-19);
.18 s, 3 H (OAc); 3.66 s, 1 H (OH); 4.01 dd, 1 H, J = 6.5, J′ = 7.2 (H-16); 4.89 and 5.09 AB
3
1
system, 2 H, J = 16.9 (2 × H-21); 5.74 s, 1 H (H-4). For C H N O (429.6) calculated: 64.30% C,
2
3
31
3
5
7
.29% H, 9.78% N; found: 64.18% C, 7.33% H, 9.59% N.
6β-Azido-17α,21-dihydroxypregn-4-ene-3,20-dione (4). Elution with a benzene–ether 1 : 1 mixture
1
+
gave 10 mg (1%) of substance 4, m.p. 199–200 °C (ethanol). Mass spectrum, m/z (%): 387 (M ,
C H N O , 0.7), 356 (0.9), 345 (0.7), 341 (2.8), 329 (1.9), 326 (3.7), 314 (3.3), 300 (25.5), 286
2
1
29
3
4
(
(
(
9.5), 272 (15.1), 243 (14.2), 231 (18.8), 211 (8.0), 205 (4.2), 201 (7.3), 197 (7.3), 187 (10.3), 173
12.9), 165 (7.0), 159 (12.9), 149 (60.6), 131 (20.4), 121 (29.6), 105 (49.3), 97 (36.6), 91 (60.6), 83
50.0), 79 (50.0), 69 (45.1), 55 (70.4), 43 (100), 41 (73.2). IR spectrum: 3 600, 3 500 (OH); 2 949,
2
854 (CH); 2 105 (N ); 1 725 (CO-20); 1 719 (N ); 1 664 (CO-3); 1 614 (C=C); 1 087 (C–O). For
3 3
C H N O (387.5) calculated: 65.08% C, 7.56% H, 10.85% N; found: 65.17% C, 7.40% H, 10.71% N.
2
1
29
3
4
3
-Oxoandrosta-4,16-diene-17-carboxamide (5). Elution with an ether–acetone 2 : 1 mixture gave
8
0 mg (10%) of substance 5, m.p. 246–247 °C (acetone), [α] +127.7° (c 0.45). Mass spectrum, m/z
D
+
(
(
%): 313 (M , C H NO , 71.0), 298 (31.2), 296 (13.5), 281 (17.7), 271 (10.6), 269 (89.4), 256
5.0), 253 (12.8), 228 (11.3), 190 (32.4), 173 (22.5), 159 (12.7), 147 (27.5), 145 (29.6), 128 (28.2),
19 (33.8), 105 (56.3), 91 (100), 79 (64.8), 77 (62.0), 67 (28.2), 55 (34.5), 44 (33.8), 41 (43.0). IR
2
0
27
2
1
spectrum: 3 532, 3 411 (NH ); 2 943, 2 861 (CH); 1 669 (CON); 1 664 (CO-3); 1 615 (C=C); 1 608
2
1
(
(
C–N); 1 578 (C=C). H NMR spectrum: 1.04 s, 3 H (3 × H-18); 1.23 s, 3 H (3 × H-19); 5.73 s, 1 H
H-4); 5.61–6.23 bs, 2 H (NH ); 6.42 t, 1 H, J = 0.7 (H-16). For C H NO (313.5) calculated:
2
20 27
2
7
6.62% C, 8.70% H, 4.47% N; found: 76.51% C, 8.48% H, 4.52% N.
Acetylation of substance 4. Azide 4 (10 mg) was dissolved in pyridine (0.2 ml), acetic anhydride
0.2 ml) was added, and the whole was allowed to stand overnight at room temperature. The reaction
(
mixture was decomposed with water and extracted with ether. The extract was treated conventionally,
and the evaporation residue was crystallized from ethanol; m.p. 181–183 °C, the RF values in TLC
using 2 systems were identical with those of substance 3. IR spectrum: 3 450 (OH); 2 950, 2 864
(
CH); 2 105 (N ); 1 745 (C–O, acetate); 1 732 (CO-20); 1 702 (N ); 1 660 (CO-3); 1 615 (C=C);
3
3
1
235 (C–O, acetate); 1 072 (C–O); 1 046 (C–O, acetate).
3
-Oxoandrosta-4,16-diene-17-carbonitrile (6)
Amide 5 (100 mg, 0.3 mmol) was dissolved in pyridine (1.5 ml), acetic anhydride (1.5 ml) was
added, and the whole was heated at 60 °C for 4 h. The mixture was decomposed with ice and ex-
tracted with chloroform, and the extract was treated conventionally. The residue was taken up in benzene
and filtered through a silica gel layer. Crystallization from a heptane–chloroform mixture gave 41 mg
3
3
(
44%) of substance 6, m.p. 154–156.5 °C (ref. : 156–158 °C), [α] +157° (c 0.24) (ref. : +168° (c 2)).
D
+
Mass spectrum, m/z (%): 295 (M , C H NO, 74.6), 280 (15.5), 267 (10.7), 253 (67.6), 238 (19.4), 224
2
0
25
(
7.0), 210 (30.7), 196 (7.0), 124 (94.4), 109 (58.9), 105 (43.7), 91 (100), 83 (29.6), 79 (65.5), 77
Collect. Czech. Chem. Commun. (Vol. 62) (1997)