Papers
405 (35), 404 (Mϩ, 100), 302 (43), 285 (49). (C24H34O4NH4
requires 404); 1H NMR (CDCl3) ␦ 0.90 (3H, s, H-18), 1.10 (3H, s,
H-19), 1.20 (9H, s, (CH3)3CCO2), 5.30 (1H, dt, J ϭ 2, 8 Hz,
H-3␣), 6.10 (1H, t, J ϭ 1 Hz, H-4); 13C NMR (CDCl3) ␦ 13.7
(C-18), 19.7 (C-19), 20.0 (C-11), 21.5 (C-15), 24.0 (C-2), 27.1 [(C
H3)3CCO2], 30.9 (C-12), 33.6 (C-8), 34.4 (C-1), 35.6 (C-16), 38.2
(C-10), 38.7 [(CH3)3CCCO2], 44.9 (C-7), 47.6 (C-13), 51.1 (C-
14), 51.5 (C-9), 68.9 (C-3), 129.8 (C-4), 147.2 (C-5), 178.1
[(CH3)3CCO2], 201.3 (C-6), 219.7 (C-17).
Further elution yielded 6-hydroxy-3-pivaloxyandrost-4-en-
17-one (405 mg, 1.04 mmol, 34%) (7d), which crystallized from
ethyl acetate as needles, m.p. 174–176°C, [␣]D ϩ 27° (c ϭ 0.10);
IR max 3475, 1724, 1153 cmϪ1; Combustion analysis: Found: C,
74.17%; H, 9.38%. (C24H36O4 requires C, 74.18%; H, 9.34%); MS
(CI NH3) m/z (%) 406 (Mϩ, 92), 371 (100), 370 (42), 287 (67),
286 (87), 269 (22), 57 (37). (C24H36O4NH4 requires 406); 1H
NMR (CDCl3) ␦ 0.94 (3H, s, H-18), 1.20 (9H, s, (CH3)3CCO2),
1.33 (3H, s, H-19), 4.29 (1H, t, J ϭ 3 Hz, H-6␣), 5.20 (1H, dt, J ϭ
2, 8 Hz, H-3␣), 5.50 (1H, s, H-4); 13C NMR (CDCl3) ␦ 13.6
(C-18), 19.9 (C-11), 21.1 (C-19), 21.5 (C-15), 24.5 (C-2), 27.0 [(C
H3)3CCO2], 29.7 (C-8), 31.2 (C-12), 35.6 (C-16), 36.4 (C-1), 36.6
(C-10), 37.8 (C-7), 38.4 [(CH3)3CCO2], 47.5 (C-13), 50.8 (C-14),
54.0 (C-9), 70.0 (C-3), 73.3 (C-6), 124.9 (C-4), 148.0 (C-5), 178.1
[(CH3)3CCO2], 220.7 (C-17).
H-3␣), 5.56 (1H, s, H-4); 13C NMR (CDCl3) ␦ 13.4 (C-18), 13.9
(CH3CH2OCO2), 19.7 (C-11), 20.8 (C-19), 21.4 (C-15), 24.4
(C-2), 29.5 (C-8), 31.0 (C-12), 35.4 (C-16), 36.0 (C-1), 36.5
(C-10), 37.4 (C-7), 47.3 (C-13), 50.6 (C-14), 53.8 (C-9), 63.5
(CH3CH2OCO2), 72.8 (C-3), 73.7 (C-6), 123.6 (C-4), 148.8 (C-5),
154.5 (CH3CH2OCO2), 220.7 (C-17).
Treibs oxidation of 3-formyloxyandrost-5-en-17-
one (9)
Mercury(II) oxide (3.42 g, 15.8 mmol) was stirred with trifluoro-
acetic anhydride (2.7 mL, 19.5 mmol) in dichloromethane. 3-
Formyloxyandrost-5-en-17-one (9) (2.00 g, 6.32 mmol) was intro-
duced after the metal oxide had dissolved. The reaction mixture
was stirred for 24 h and filtered through celite to remove the
mercurous deposits. The filtrate was washed with saturated sodium
bicarbonate solution and was dried. The solvent was evaporated in
vacuo and the resultant yellow-brown foam (2.24 g) was chro-
matographed. Elution with 20% ethyl acetate in petrol gave unre-
acted starting material (124 mg, 0.391 mmol, 6.2%) and later
afforded 3,6-diformyloxyandrost-4-en-17-one (12) (50 mg,
0.139 mmol, 2.2%), which crystallized from ethyl acetate-petrol as
needles, m.p. 154–155°C, [␣]D ϩ 60° (c ϭ 0.10); IR
1720,
max
1700, 1190 cmϪ1; Combustion analysis: Found: C, 69.59%; H,
7.86%. (C21H28O5 requires C, 69.96%; H, 7.83%); MS (CI NH3)
m/z (%) 378 (Mϩ, 51), 315 (100), 314 (55), 269 (86).
(C21H28O5NH4 requires 378); 1H NMR (CDCl3) ␦ 0.90 (3H, s,
H-18), 1.21 (3H, s, H-19), 5.40 (1H, t, J ϭ 7 Hz, H-3␣), 5.46 (1H,
s, H-6␣), 5.68 (1H, s, H-4), 8.06 (2H, s, CHO-3, 6); 13C NMR
(CDCl3) ␦ 13.8 (C-18), 20.0 (C-11), 20.5 (C-19), 21.7 (C-15), 24.6
(C-2), 30.4 (C-8), 31.2 (C-12), 35.7 (C-16), 35.9 (C-7), 36.3 (C-1),
36.8 (C-10), 47.6 (C-13), 50.8 (C-14), 53.7 (C-9), 69.8 (C-3), 74.6
(C-6), 127.9 (C-4), 143.8 (C-5), 160.1 (CHO-6),* 160.7 (CHO-
3),* 220.3 (C-17). (* ϭ interchangeable assignments).
Treibs oxidation of 3-carboethoxyandrost-5-en-17-
one (1e)
Mercury(II) oxide (3.0 g, 13.87 mmol) and trifluoroacetic anhy-
dride (2.4 mL, 16.9 mmol) were stirred together in dichlorometh-
ane (200 mL). 3-Carboethoxyandrost-5-en-17-one (1e) (2.00 g,
5.55 mmol) was added and the solution was stirred for 24 h. The
reaction mixture was filtered through celite to remove the off-
white mercury(I) deposits. The lime green filtrate was washed with
saturated sodium hydrogen carbonate solution and dried. Evapo-
ration of the solvent under reduced pressure gave a brown foam
(2.5 g), which was chromatographed. Elution with 10% ethyl
acetate in petrol afforded unreacted starting material (99 mg, 0.275
mmol, 5.0%). Further elution (15% ethyl acetate in petrol) gave
3-carboethoxy-6-chloromercuriandrost-5-en-17-one (4e) (213 mg,
0.358 mmol, 6.5%), which crystallized from methanol as rectangular
prisms, m.p. 210–211°C, [␣]D Ϫ 26° (c ϭ 0.10); IR max 1737, 1254
Further elution produced androst-4-ene-3,17-dione (15) (20
mg, 0.070 mmol, 1.1%), which was recrystallized from acetone to
give cuboids, m.p. 166–167°C, [␣]D ϩ 197° (c ϭ 0.10), lit.17 m.p.
169–170°C, [␣]D ϩ 205° (c ϭ 0.10); UV (EtOH)
235 nm,
max
log ϭ 4.15; IR max 1738, 1661 cmϪ1; 1H NMR (CDCl3) ␦ 0.98
(3H, s, H-18), 1.28 (3H, s, H-19), 5.75 (1H, s, H-4); 13C NMR
(CDCl3) ␦ 13.5 (C-18), 17.2 (C-19), 20.1 (C-11), 21.6 (C-15), 30.6
(C-12), 31.1 (C-7), 32.4 (C-6), 33.7 (C-2), 35.0 (C-8), 35.5 (C-1),*
35.6 (C-16),* 38.5 (C-10), 47.3 (C-13), 50.7 (C-14), 53.6 (C-9),
123.9 (C-4), 170.3 (C-5), 199.2 (C-3), 220.3 (C-17). (* ϭ inter-
changeable assignments).
cmϪ1
; Combustion analysis: Found: C, 44.48%; H, 5.37%.
(C22H31ClHgO4 requires C, 44.37%; H, 5.25%); MS (CI NH3) m/z
(%) 616 (1), 615 (1), 614 (Mϩ, 2), 613 (1), 612 (2), 611 (2), 269 (6),
157 (57), 96 (52), 79 (100). (C22H3135Cl202HgO4NH4 requires 614);
1H NMR (CDCl3) ␦ 0.88 (3H, s, H-18), 1.13 (3H, s, H-19), 1.33 (3H,
t, J ϭ 7.5 Hz, CH3CH2OCO2), 4.20 (2H, q, J ϭ 7.5 Hz,
CH3CH2OCO2), 4.54 (1H, m, w/2 ϭ 22 Hz, H-3␣); 13C NMR
(CDCl3) ␦ 13.5 (C-18), 14.2 (CH3CH2OCO2), 20.0 (C-19), 20.2
(C-11), 21.8 (C-15), 27.3 (C-2), 31.2 (C-12), 32.7 (C-8), 35.7 (C-16),
36.8 (C-1), 40.0 (C-7), 40.0 (C-10), 43.7 (C-4), 47.4 (C-13), 49.6
(C-9), 51.4 (C-14), 63.8 (CH3CH2OCO2), 76.5 (C-3), 147.4 (C-5),*
147.7 (C-6),* 154.2 (CH3CH2OCO2), 220.6 (C-17). (* ϭ inter-
changeable assignments).
Elution with 30% ethyl acetate in petrol yielded 3-
carboethoxy-6-hydroxyandrost-4-en-17-one (7e) (409 mg, 1.09
mmol, 20%), which crystallized from ethyl acetate as rectangular
prisms, m.p. 183.5–184.5°C, [␣]D ϩ 35° (c ϭ 0.07); IR max 3469,
1747, 1725, 1259 cmϪ1; Combustion analysis: Found: C, 70.07%;
H, 8.81%. (C22H32O5 requires C, 70.17%; H, 8.57%); MS (CI
NH3) m/z (%) 394 (Mϩ, 78), 358 (39), 287 (58), 286 (100).
(C22H32O5NH4 requires 394); 1H NMR (CDCl3) ␦ 0.92 (3H, s,
Elution with 30% ethyl acetate in petrol gave 3-formyloxy-
6-hydroxyandrost-4-en-17-one (10) (328 mg, 0.987 mmol, 16%),
which crystallized from ethyl acetate-petrol as small cuboids, m.p.
152–154°C, [␣]D ϩ 33° (c ϭ 0.11); IR
3375, 1725, 1715,
max
1170 cmϪ1; MS (EI), m/z (%) 332.1983 (1), 314.1879 (5),
286.1932 (100), 271.1698 (53), 93.0705 (23), 91.0548 (22).
1
(C20H28O4 requires 332.1988); H NMR (CDCl3) ␦ 0.90 (3H, s,
H-18), 1.30 (3H, s, H-19), 4.26 (1H, s, H-6␣), 5.36 (1H, t, J ϭ 9
Hz, H-3␣), 5.50 (1H, s, H-4), 8.09 (1H, s, CHO); 13C NMR
(CDCl3) ␦ 13.8 (C-18), 20.1 (C-11), 21.3 (C-19), 21.7 (C-15), 24.8
(C-2), 29.8 (C-8), 31.3 (C-12), 35.8 (C-16), 36.4 (C-1), 36.8
(C-10), 37.7 (C-7), 47.7 (C-13), 51.1 (C-14), 54.1 (C-9), 70.3
(C-3), 73.5 (C-6), 124.3 (C-4), 149.4 (C-5), 160.8 (CHO), 220.8
(C-17). The isomeric but slightly more polar 6-formyloxy-3-
hydroxyandrost-4-en-17-one (13) (37 mg, 0.111 mmol, 1.8%) was
also obtained and crystallized from ethyl acetate as wispy needles,
m.p. 194–196°C, [␣]D ϩ 119° (c ϭ 0.07); IR
3500, 1730,
max
1200 cmϪ1; MS (CI NH3) m/z (%) 350 (Mϩ, 100), 315 (24), 286
(29), 269 (26), (C20H28O4NH4 requires 350); MS (EI) m/z (%)
286.1933 (100), 271.1698 (16), 177.1279 (13), 105.0705 (14),
91.0548 (18), 79.0547 (15). (C20H28O4 Ϫ HCO2H requires
H-18), 1.29 (3H, s, H-19), 1.30 (3H, t,
J ϭ 7.5 Hz,
CH3CH2OCO2), 2.65 (1H, b s, HO), 4.20 (2H, q, J ϭ 7.5 Hz,
CH3CH2OCO2), 4.26 (1H, b s, H-6␣), 5.10 (1H, t, J ϭ 8 Hz,
654 Steroids, 1998, vol. 63, December