On Steroids
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was poured on to ice (300 m l), th e precipitate was extracted with eth yl acetate (3 × 150 m l)
an d wash ed with a cold solution of sodium h ydroxide (0 °C, 2%) an d water. Th e solven t was
rem oved in vacuum an d ch rom atograph y of th e residue on silica gel (250 g, toluen e) yielded
th e β-lacton e 6 (19.4 g, 90%); [α]D +10 (c 1.2). Circular dich roism : ∆ε227 +0.33, ∆ε243 –0.70
(m eth an ol). IR: 1 819 (β-lacton e); 1 726, 1 254, 1 038 (AcO); 1 709, 1 288, 1 275, 962, 714
(ben zoate); 1 603, 1 315, 1 108, 1 027 (arom .). 1H NMR: 8.05 m , 2 H (H-2′ an d H-6′); 7.60 t,
1 H (J = 7.2, H-4′); 7.49 t, 2 H (J = 7.3, H-3′ an d H-5′); 5.18 m , 1 H (W = 36, H-20); 5.00 m ,
1 H (W = 35, H-3); 3.19 d, 1 H (J(6α,8β) = 13.7, H-7); 2.05 s, 3 H (CH3CO); 1.28 d, 3 H (J =
6.2, 3 × H-21); 0.97 s, 3 H (3 × H-19); 0.70 s, 3 H (3 × H-18). For C30H38O6 (494.6) calculated:
72.85% C, 7.74% H; foun d: 72.76% C, 7.73% H.
(20R)-7-Norpregn -5-en e-3β,20-diyl 3-Acetate 20-Ben zoate (7)
A solution of com poun d 6 (18.4 g, 37.2 m m ol) in toluen e (200 m l) was h eated at reflux
tem perature un der n itrogen for 95 h an d th en th e solven t was evaporated in vacuum . Ch ro-
m atograph y of th e residue on silica gel (250 g, toluen e) gave 13.1 g (78%) of com poun d 7;
m .p. 117–118 °C (m eth an ol), [α]D –73 (c 1.1). IR: 3 072, 3 064, 3 028, 3 012 (C=C–H); 1 727,
1 602, 1 585, 1 279, 961 (ben zoate); 1 708 (C=O); 1 252, 1 027 (acetate); 1 653 (C=C).
1H NMR: 8.05 m , 2 H (H-2′ an d H-6′); 7.60 t, 1 H (J = 7.2, H-4′); 7.49 t, 2 H (J = 7.3, H-3′ an d
H-5′); 5.40 bs, 1 H (W = 10.0, H-6); 5.18 m , 1 H (W = 36, H-20); 4.64 m , 1 H (W = 35, H-3);
2.63 ddd, 1 H (J(4α,4β) = 13.7, J(4α,3α) = 4.9, J(4α,6) = 1.8, H-4α); 2.04 s, 3 H (CH3CO);
0.86 s, 3 H (3 × H-19); 0.64 s, 3 H (3 × H-18). MS, m/z (%): 450 (M+, 0.2), 406 (0.6), 390 (15),
268 (65), 253 (19), 239 (11). For C29H38O4 (450.6) calculated: 77.30% C, 8.50% H; foun d:
77.24% C, 8.47% H.
(20R)-7-Nor-5α-pregn an e-3β,20-diyl 3-Acetate 20-Ben zoate (8)
Method A. A m ixture of alken e 7 (207 m g, 0.46 m m ol) an d tosylh ydrazin e (610 m g, 3.28
m m ol) was h eated in 2,4,6-trim eth ylpyridin e (3.0 m l) at 150 °C. After 3 h , th e solven t was
evaporated, th e residue was dissolved in eth er an d th e eth ereal solution was wash ed succes-
sively with th e solution of h ydroch loric acid, water an d th e solution of potassium carbon ate
an d water. Th e solution was th en dried with an h ydrous sodium sulfate an d th e solven t was
evaporated. Th in layer ch rom atograph y of th e residue (4 PLC plates, ben zen e–eth er 10 : 1)
gave com poun d 8 (182 m g, 88%); m .p. 144–145 °C (m eth an ol), [α]D –37 (c 1.0). IR: 3 092,
3 072, 3 064, 1 603, 1 585, 1 451, 1 120 (arom .); 1 709, 1 285, 972 (ben zoate); 1 709, 1 249,
1 042 (AcO). 1H NMR: 8.04 m , 2 H (W = 16, H-2′ and H-6′); 7.79 m , 1 H (W = 20, H-4′); 7.44 m ,
2 H (W = 20, H-3′ an d H-5′); 5.15 m , 1 H (W = 36, H-20); 4.72 m , 1 H (W = 39, H-3); 2.02 s,
3 H (CH3CO); 1.27 d, 3 H (J = 6.1, H-21); 0.70 s, 3 H (3 × H-19); 0.66 s, 3 H (3 × H-18). For
C
29H40O4 (452.6) calculated: 76.95% C, 8.91% H; foun d: 76.70% C, 9.03% H.
Method B. Alken e 7 (3.09 g, 6.86 m m ol) was treated with tosylh ydrazin e (9.7 g, 52.1
m m ol) in 2,4,6-trim eth ylpyridin e (50 m l) as above. Th e product was dissolved in dich loro-
m eth an e (30 m l) an d treated with 3-ch loroperoxyben zoic acid (0.5 g, 2.9 m m ol) at room
tem perature. After 3 h , th e solution was wash ed with th e potassium carbon ate solution an d
water an d con cen trated in vacuum on a rotary evaporator. Th e solution was applied on a
colum n of silica gel (100 g). A m ixture of ligroin –toluen e (2 : 1) eluted com poun d 8 (2.5 g,
81%) iden tical with th e above described sam ple. Furth er fraction s yielded (20R)-5,6α-ep-
oxy-7-n or-5α-pregn an e-3β,20-diyl 3-acetate 20-ben zoate (9, 0.55 g, 17%); m .p. 204–206 °C
Collect. Czech. Chem. Commun. (Vol. 64) (1999)