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3.1.13.2.
2-Ethoxy-3-cyano-6-(4-methylphenyl)and-
2H, CH2-ethoxy), 7.23–7.42 (m, 4H, Ar-H); MS m/z
(%): 486 [M+, 100, base peak), corresponding to the
molecular formula C31H35FN2O2.
rostano[17,16-d]pyridine-3b-ol (15b). Yield 64%; mp
216 °C (EtOH); IR (KBr, cmꢀ1): 3517–3491 (OH),
1
2249 (CN); H NMR (DMSO-d6): d 0.74 (s, 3H, CH3,
C19), 0.82 (s, 3H, CH3, C18), 0.94–0.98 (m, 1H, CH),
1.18–1.24 (m, 4H, 2CH2), 1.37–1.52 (m, 6H, 3CH2),
1.57 (t, 3H, CH3-ethoxy), 1.62–1.85 (m, 4H, 2CH2),
1.94–1.98 (m, 1H, CH), 2.26–2.38 (m, 2H, CH2), 2.43
(s, 3H, Ph–CH3), 2.50–2.55 (m, 1H, CH), 3.00–3.10
(m, 1H, 5a-CH), 3.50–3.56 (m, 1H, 3a-CH), 4.43 (q,
2H, CH2-ethoxy), 7.22–7.46 (m, 4H, Ar-H), 10.06 (s,
1H, OH, exchangeable with D2O); MS m/z (%): 484
(M+, 100), corresponding to the molecular formula
C32H40N2O2 and also as base peak.
3.1.15.2.
2-Ethoxy-3-cyano-6-(4-methylphenyl)and-
rostano[17,16-d]pyridine-3-one (17b). Yield 54%; mp
217 °C (EtOH/EtOAc); IR (KBr, cmꢀ1): 2246 (CN),
1728 (C@O); 1H NMR (DMSO-d6): d 0.77 (s, 3H,
CH3, C19), 0.86 (s, 3H, CH3, C18), 0.98–1.15 (m, 1H,
CH), 1.22–1.34 (m, 4H, 2CH2), 1.45–1.55 (m, 6H,
3CH2), 1.57 (t, 3H, CH3-ethoxy), 1.65–1.94 (m, 4H,
2CH2), 2.00–2.10 (m, 1H, CH), 2.32–2.40 (m, 2H,
CH2), 2.45 (s, 3H, Ph–CH3), 2.48–2.56 (m, 1H, CH),
3.00–3.15 (m, 1H, 5a-CH), 4.46 (q, 2H, CH2-ethoxy),
7.23–7.41 (m, 4H, Ar-H); MS m/z (%): 482 (M+, 10),
corresponding to the molecular formula C32H38N2O2
and at 296 (100, base peak).
3.1.14. Synthesis of 2-ethoxy-3-cyano-6-(4-substituted
phenyl)androst-3-ene[17,16-d]pyridines (16a,b). Com-
pounds 16a,b were prepared by the method given for com-
pounds 4 using compound 15a,b as starting materials.
3.1.16. Synthesis of 2-ethoxy-3-cyano-6-(4-substituted
phenyl)androst-1,4-diene[17,16-d]pyridine-3-ones (18a,b).
Anhydrous hydrogen chloride gas was bubbled into
a solution of compounds 17a,b (6 mmol) and 2,3-
dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (1.8 g)
in dioxane (40 mL). The reaction mixture was kept
for 30 min at room temperature, the precipitated
hydroquinone removed by filtration. The filtrate
was extracted by ether, the ethereal solution washed
with 1% sodium hydroxide then with water and
dried over sodium sulfate anhydrous. The solvent
was evaporated under reduced pressure, the residue
formed was crystallized from ethanol to give the cor-
3.1.14.1. 2-Ethoxy-3-cyano-6-(4-fluorophenyl)androst-
3-ene[17,16-d]pyridine (16a). Yield 56%; mp 307 °C
(MeOH); IR (KBr, cmꢀ1): 2268 (CN); 1H NMR
(DMSO-d6): d 0.76 (s, 3H, CH3, C19), 0.82 (s, 3H, CH3,
C18), 0.92–0.96 (m, 1H, CH), 1.18–1.25 (m, 4H, 2CH2),
1.41–1.55 (m, 4H, 2CH2), 1.59 (t, 3H, CH3-ethoxy),
1.62–1.78 (m, 4H, 2CH2), 1.86–1.98 (m, 1H, CH),
2.27–2.39 (m, 2H, CH2), 2.50–2.57 (m, 1H, CH), 3.16–
3.25 (m, 1H, CH, C5), 4.40 (q, 2H, CH2-ethoxy), 5.29–
5.34 (m, 1H, CH, C3), 5.50 (d, 1H, CH, C4), 7.24–7.37
(m, 4H, Ar-H); MS m/z (%): 470 (M+, 15), corresponding
to the molecular formula C31H35FN2O and at 280 (100,
base peak).
responding
respectively.
cyclohexyldiene
derivatives
18a,b,
3.1.14.2.
2-Ethoxy-3-cyano-6-(4-methylphenyl)and-
3.1.16.1. 2-Ethoxy-3-cyano-6-(4-fluorophenyl)androst-
1,4-diene[17,16-d]pyridine-3-one (18a). Yield 55%; mp
321 °C (EtOH); IR (KBr, cmꢀ1): 2251 (CN), 1780–
1765 (CO, enone); 1H NMR (DMSO-d6): d 0.78 (s,
3H, CH3, C19), 0.85 (s, 3H, CH3, C18), 0.98–1.05
(m, 1H, CH), 1.26–1.31 (m, 4H, 2CH2), 1.44–1.54
(m, 2H, CH2), 1.58 (t, 3H, CH3-ethoxy), 1.64–1.75
(m, 2H, CH2), 1.80–1.88 (m, 1H, CH), 1.95–2.05 (m,
2H, CH2), 2.32–2.41 (m, 1H, CH), 4.44 (q, 2H,
CH2-ethoxy), 5.70 (d, 1H, CH, C4), 5.98 (s, 1H,
CH, C2), 7.00 (d, 1H, CH, C1), 7.22–7.34 (m, 4H,
Ar-H); MS m/z (%): 482 (45) [M+], corresponding to
the molecular formula C31H31FN2O2 and at 292
(100, base peak).
rost-3-ene[17,16-d]pyridine- 3b-ol (16b). Yield 68%; mp
277 °C (EtOH); IR (KBr, cmꢀ1): 2248 (CN); 1H
NMR (DMSO-d6): d 0.78 (s, 3H, CH3, C19), 0.83 (s,
3H, CH3, C18), 0.92–0.98 (m, 1H, CH), 1.08–1.26 (m,
4H, 2CH2), 1.34–1.54 (m, 4H, 2CH2), 1.57 (t, 3H,
CH3-ethoxy), 1.66–1.85 (m, 4H, 2CH2), 1.88–1.95 (m,
1H, CH), 2.23–2.42 (m, 2H, CH2), 2.46 (s, 3H, Ph–
CH3), 2.53–2.57 (m, 1H, CH), 3.25–3.35 (m, 1H, CH,
C5), 4.40 (q, 2H, CH2-ethoxy), 5.26–5.40 (m, 1H,
CH, C3), 5.48 (d, 1H, CH, C4), 7.22–7.34 (m, 4H,
Ar-H); MS m/z (%): 466 (M+, 15), corresponding to
the molecular formula C32H38N2O and at 280 (100,
base peak).
3.1.15. Synthesis of 2-ethoxy-3-cyano-6-(4-substituted
phenyl)androstano[17,16-d]pyridine-3-ones (17a,b). Com-
pounds 17a,b were prepared by the method given for com-
pounds 5 using compound 15a,b as starting materials.
3.1.16.2.
2-Ethoxy-3-cyano-6-(4-methylphenyl)and-
rost-1,4-diene[17,16-d]pyridine-3-one (18b). Yield 53%;
mp 311 °C (EtOH); IR (KBr, cmꢀ1): 2248 (CN),
1771–1785 (C@O, enone); 1H NMR (DMSO-d6): d
0.77 (s, 3H, CH3, C19), 0.87 (s, 3H, CH3, C18),
1.10–1.16 (m, 1H, CH), 1.24–1.32 (m, 4H, 2CH2),
1.44–1.56 (m, 2H, CH2), 1.60 (t, 3H, CH3-ethoxy),
1.64–1.72 (m, 2H, CH2), 1.78–1.87 (m, 1H, CH),
1.95–2.00 (m, 2H, CH2), 2.33–2.44 (m, 1H, CH),
2.46 (s, 3H, Ph–CH3), 4.50 (q, 2H, CH2-ethoxy),
5.68 (d, 1H, CH, C4), 6.00 (s, 1H, CH, C2), 6.96 (d,
1H, CH, C1), 7.23–7.35 (m, 4H, Ar-H); MS m/z (%):
478 (M+, 100, base peak), corresponding to the molec-
ular formula C32H34N2O2.
3.1.15.1. 2-Ethoxy-3-cyano-6-(4-fluorophenyl)androst-
ano[17,16-d]pyridine-3-one (17a). Yield 66%; mp 157 °C
(EtOH/EtOAc); IR (KBr, cmꢀ1): 2251 (CN), 1723
(C@O); 1H NMR (DMSO-d6): d 0.76 (s, 3H, CH3,
C19), 0.86 (s, 3H, CH3, C18), 1.00–1.15 (m, 1H, CH),
1.25–1.29 (m, 4H, 2CH2), 1.39–1.56 (m, 6H, 3CH2),
1.60 (t, 3H, CH3-ethoxy), 1.66–1.90 (m, 4H, 2CH2),
1.97–2.00 (m, 1H, CH), 2.25–2.42 (m, 2H, CH2), 2.49–
2.54 (m, 1H, CH), 2.99–3.10 (m, 1H, 5a-CH), 4.44 (q,