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A. Kasal et al. / Steroids 67 (2002) 57–70
acid (10 ml). The product was applied onto 5 PLC plates
that were developed with benzene-ether (5:1). The follow-
ing compounds were isolated:
2.20. 5-Methyl-19-nor-5-androst-9-ene-3␣,17-diyl 3-
pivalate 17-acetate (32)
3␣-Hydroxy-5-methyl-19-nor-5,9,10-androstan-
17-yl cyclohexanecarboxylate (42) (10 mg, 5%), m.p. 136–
138°C (acetone-heptane); [␣]D ϩ2° (c 0.9); IR spectrum
Compound 30 (260 mg, 0.78 mmol) was treated with
trimethylacetylchloride in pyridine as in the preceding ex-
periment. The product was purified by PLC (9 plates, ben-
zene-ether 20:1). Yield: 297 mg (91%); [␣]D ϩ69° (c 0.9);
IR spectrum: 1716 (C ϭ O), 1398, 1365, 1172 (t-butyl),
1
(CCl4): 3619 (OH), 1730 (C ϭ O), 1171, 1041 (C-O). H
NMR spectrum: 4.68 t (Jϳ8.5, 17-H), 4.08 m (3-H), 0.97 s
(5-Me), 0.82 s (13-Me). EI-MS, m/z (%): 384 (64), 369 (14),
274 (31), 256 (100), 241 (28), 215 (28); HR-MS (FAB): for
C26H43O3 required 403.321221, found 403.315100.
A mixture of 3␣-hydroxy-5-methyl-19-nor-5,9␣,10-
androstan-17-yl cyclohexanecarboxylate (40) and 3␣-hy-
droxy-5-methyl-19-nor-5,9,10␣-androstan-17-yl cyclo-
hexanecarboxylate (41, 168 mg, 84%); [␣]D ϩ24° (c 0.9);
1H NMR spectra, compound 40: 4.62 t (Jϳ8.5, 17-H),
3.91 m (3-H), 0.99 s (5-Me), 0.80 s (13-Me) and compound
41: 4.71 t (Jϳ8.5, 17-H), 3.85 m (3-H), 0.86 s (5-Me),
0.82 s (13-Me).
1
1388, 1373 (methyl), 1288, 1258, 1030 (C-O); H NMR
spectrum: 5.07 (3-H), 4.61 m t (Jϳ8.5, 17-H), 2.04 s (OAc),
1.17 s (Piv), 1.09 s (5-Me), 0.91 s (13-Me). For C26H40O4
(416.6) calcd: 74.96% C, 9.68% H; found: 74.56% C,
9.46% H.
2.21. Hydrogenation of 5-methyl-19-nor-5-androst-9-
ene-3,17-diyl 3-pivalate 17-acetate (31)
Compound 31 (502 mg, 1.20 mmol) was hydrogenated
as above, and PLC plates (11) were developed with ben-
zene-ether (20:1). The following compounds were isolated:
5-Methyl-19-nor-5,9,10-androstane-3,17-diyl 3-piv-
alate 17-acetate (10) (259 mg, 51%), m.p. 118–119°C
(CH3OH); [␣]D –5° (c 0.9); IR spectrum: 1716, 1725 (C ϭ
O), 1287, 1257 (C-O), 1374 (CH3 in CH3COO), 1178, 1160
2.18. Hydrogenation of 3␣-hydroxy-5-methyl-19-nor-5-
androst-9-en-17-yl acetate (30)
Compound 30 (80 mg, 0.24 mmol) was hydrogenated as
above, PLC (4 plates, benzene-ether 4:1) yielded the fol-
lowing fractions:
1
(CH3 in (CH3)3COO); H NMR spectrum: 4.77 m (3-H),
4.65 t (Jϳ8.5, 17-H), 2.03 s (OAc), 1.17 s (Piv), 1.01 s
(5-Me), 0.79 s (13-Me). For C26H42O4 (418.6) calcd:
74.60% C, 10.11% H; found: 74.80% C, 10.28% H.
A mixture of 5-methyl-19-nor-5,9␣,10-androstane-
3,17-diyl 3-pivalate 17-acetate (46) and 5-methyl-19-
nor-5,9,10␣-androstane-3,17-diyl 3-pivalate 17-
3␣-Hydroxy-5-methyl-19-nor-5,9,10-androstan-
17-yl acetate (45, 6 mg, 7%), oil; 1H NMR spectrum: 4.68 t
(Jϳ8.5, 17-H), 4.06 m (3-H), 0.96 s (5-Me), 0.80 s (13-Me).
3␣-Hydroxy-5-methyl-19-nor-5,9␣,10-androstan-
17-yl acetate (43, 59 mg, 70%), m.p. 160–161°C (acetone-
heptane); [␣]D ϩ30° (c 0.7); IR spectrum: 3606 (OH), 1724
(C ϭ O), 1259, 1045 (C-O), 1025 (C-OH); 1H NMR spectrum:
4.60 t (Jϳ8.5, 17-H), 3.90 m (3-H), 2.03 s (OAc), 0.97 s
(5-Me), 0.78 s (13-Me). For C21H34O3 (334.5) calcd: 75.41%
C, 10.25% H; found: 75.26% C, 10.22% H.
1
acetate (47) (199 mg, 39%). H NMR spectra, compound
46: 5.08 m (3-H), 4.60 dd t (Jϳ8.5, 17-H), 2.04 s (OAc),
1.19 s (Piv), 1.14 s (5-Me), 0.79 s (13-Me); compound 47:
5.04 m (3-H), 4.71 t (Jϳ8.5, 17-H), 2.04 s (OAc), 1.19 s
(Piv), 1.02 s (5-Me), 0.81 s (13-Me).
3␣-Hydroxy-5-methyl-19-nor-5,9,10␣-androstan-
1
17-yl acetate (44, 19 mg, 23%), oil; H NMR spectrum:
2.22. Hydrogenation of 5-methyl-19-nor-5-androst-9-
ene-3␣,17-diyl 3-pivalate 17-acetate (32)
4.71 t (Jϳ8.5, 17-H), 2.04 s (OAc), 3.83 m (3-H), 0.85 s
(5-Me), 0.81 s (13-Me).
Compound 32 (270 mg, 0.65 mmol) was hydrogenated
as above, and the product was applied onto 8 PLC plates,
which were developed with benzene-ether (20:1). The fol-
lowing compounds were isolated:
2.19. 5-Methyl-19-nor-5-androst-9-ene-3,17-diyl 3-
pivalate 17-acetate (31)
Trimethylacetylchloride (1.5 ml, 12.18 mmol) was added
to a solution of compound 28 (900 mg, 2.69 mmol) in
pyridine (3 ml) at 0°C. The solution was left aside for 8 h at
20°C and then poured onto ice. The resulting precipitate
was extracted into chloroform and washed successively
with a solution of hydrochloric acid, water, potassium hy-
drogen carbonate solution, and water. The product crystal-
lized from ethanol, m.p. 111–113°C (838 mg, 74%); [␣]D
A mixture of 5-methyl-19-nor-5,9␣,10-androstane-
3,17-diyl 3␣-pivalate 17-acetate (48) and 5-methyl-19-
nor-5,9,10␣-androstane-3␣,17-diyl 3-pivalate 17-ace-
1
tate (49) (175 mg, 65%); H NMR spectra, compound 48:
4.92 m (3-H), 4.61 t (Jϳ8.5, 17-H), 2.04 s (OAc), 1.18 s
(Piv), 1.03 s (5-Me), 0.78 s (13-Me) and compound 49:
4.97 m (3-H), 4.70 t (Jϳ8.5, 17-H), 2.04 s (OAc), 0.90 s
(5-Me), 0.80 s (13-Me).
5-Methyl-19-nor-5,9,10-androstane-3␣,17-diyl 3-
pivalate 17-acetate (50) (67 mg, 25%), m.p. 99–100°C
(acetone-heptane); [␣]D–1° (c 1.2); IR spectrum: 1716 (C ϭ
O), 1374 (CH3 in CH3COO), 1288, 1257 (C-O), 1173, 1155
1
ϩ69° (c 1.2); H NMR spectrum: 5.06 m (3-H), 4.60 t
(Jϳ8.5, 17-H), 1.22 s (Piv); 1.21 s (5-Me), 0.91 s (13-Me).
For C26H40O4 (416.6) calcd: 74.96% C, 9.68% H; found:
74.96% C, 9.60% H.