Preparation of Steroid Sulfamates
649
h ydroxide pellets to afford com poun d 4 (79 m g, 64%). M.p. 154–156 °C, [α]D was n ot m ea-
sured due to a low solubility of th e sam ple. IR (KBr): 3347, 3239 (NH ); 1696 (C=O); 1385,
2
1
1
367, 1191 (SO ); 929 (C–O); 898 (N–S). H NMR: 4.89 m , 1 H, W1/2 = 4 (H-3); 4.64 s, 2 H
2
(
(
NH ); 2.54 t, 1 H, J = 8.8 (H-17); 2.11 s, 3 H (3 × H-21); 0.79 s, 3 H (3 × H-19); 0.60 s, 3 H
2
3 × H-18). For C21H35NO S (397.6) calculated: 63.44% C, 8.87% H, 3.52% N, 8.07% S;
4
foun d: 62.42% C, 9.11% H, 3.57% N, 8.22% S.
0-Oxo-5α-pregnan-3β-yl sulfamate (5). Hydroxy derivative 1 (150 m g, 0.471 m m ol) was
2
con verted in to 5 accordin g to Gen eral Procedure. After workup, th e product was separated
on a colum n of silica gel (12 g), wh ich was prewash ed with 2% trieth ylam in e in ben zen e.
Ben zen e with an in creasin g am oun t of eth yl acetate (2–12%) was used as th e eluen t. Crystal-
lization from petroleum eth er an d aceton e yielded 5 as wh ite crystals (80 m g, 43%). M.p.
1
1
58–160 °C, [α]D +46.1 (c 0.25). IR (CHCl ): 3443, 3351 (NH ); 1698 (C=O); 1382, 1361,
3 2
1
182 (SO ); 947, 939 (C–O); 916 (N–S). H NMR: 4.71 s, 2 H (NH ); 4.53 m , 1 H, W = 19
1/2
2
2
(
(
H-3); 2.52 t, 1 H, J = 9.1 (H-17); 2.12 s, 3 H (3 × H-21); 0.83 s, 3 H (3 × H-19); 0.60 s, 3 H
3 × H-18). For C21H35NO S (397.6) calculated: 63.44% C, 8.87% H, 3.52% N, 8.07% S;
4
foun d: 63.47% C, 9.2% H, 3.37% N, 7.71% S.
0-Oxo-5β-pregnan-3α-yl sulfamate (7). Hydroxy derivative8 6 (320 m g, 1.0 m m ol) was con -
2
verted in to 7 accordin g to Gen eral Procedure. After workup, ch rom atograph y on a silica gel
colum n (15 g) in petroleum eth er–aceton e (8:2) yielded com poun d 7 (225 m g, 56%). M.p.
1
1
4
70–173 °C (h eptan e–dich lorom eth an e), [α]D +92.8 (c 0.23). IR (CHCl ): 3347, 3351 (NH );
3 2
1
700 (C=O); 1380, 1362, 1181 (SO ); 943, 933 (C–O); 912 (N–S). H NMR: 4.71 s, 2 H (NH );
2
2
.58 m , 1 H, W1/2 = 19 (H-3); 2.54 t, 1 H, J = 9.0 (H-17); 2.12 s, 3 H (3 × H-21); 0.94 s, 3 H
(
3 × H-19); 0.60 s, 3 H (3 × H-18). For C21H35NO S (397.6) calculated: 63.44% C, 8.87% H;
4
3
.52% N, 8.07% S; foun d: 61.84% C, 8.82% H; 3.22% N, 7.91% S.
0-Oxo-5β-pregnan-3β-yl sulfamate (9). Hydroxy derivative8 8 (306 m g, 0.96 m m ol) was
2
con verted in to 9 accordin g to Gen eral Procedure. After workup, th e product was separated
on a silica gel colum n (18 g), wh ich was prewash ed with 2% trieth ylam in e in ben zen e. Ben -
zen e with an in creasin g am oun t of eth yl acetate (2–12%) was used as th e eluen t. Crystalliza-
tion from eth an ol an d water yielded 9 as wh ite crystals, wh ich were dried in a desiccator
over sodium h ydroxide pellets (0.153 g, 40%). M.p. 169–172 °C, [α]D +70.4 (c 0.27). IR
(
1
CHCl ): 3341, 3350 (NH ), 1698 (C=O); 1385, 1365, 1183 (SO ); 924 (C–O); 913 (N–S).
3 2 2
H NMR: 4.97 m , 1 H (H-3); 4.71 m , 2 H (NH ); 2.53 t, 1 H, J = 9.1 (H-17); 2.11 s, 3 H (3 ×
2
H-21); 0.98 s, 3 H (3 × H-19); 0.61 s, 3 H (3 × H-18). For C21H35NO S (397.6) calculated:
4
6
3.44% C, 8.87% H, 3.52% N, 8.07% S; foun d: 62.81% C, 9.13% H, 3.30% N, 7.99% S.
2
0-Oxo-5α-pregn an -3α-yl Sulfate Pyridin ium Salt (10)
Hydroxy derivative 3 (159 m g, 0.5 m m ol) an d sulfur trioxide–pyridin e com plex (398 m g,
2
.5 m m ol) in fresh ly distilled ch loroform (10 m l) were stirred at room tem perature un der
argon for 4 h . Th e m ixture was cooled to –18 °C, filtered, an d th e solven t was rem oved
un der reduced pressure. Th e resultin g crude product was dissolved in ch loroform (2 m l),
ch illed in a freezer for a sh ort tim e, an d th e precipitate of sulfur trioxide–pyridin e com plex
was rem oved. Ligh t petroleum (7 m l) was added to th e filtrate an d after keepin g at room
tem perature for 2 h , steroid pyridin ium sulfate was collected. M.p. 181–183 °C, [α] +69.0
D
1
4
(
(
(
c 0.21). Literature gives m .p. 184 °C, [α]D +70.0. IR (CHCl ): 3139 (pyridin ium ); 1698
C=O, keton e); 1270, 1257, 1236, 1179, 1166 (SO3 an d pyridin ium ). H NMR: 9.00 m , 2 H
3
1
H-2 an d H-6, pyridin ium ); 8.50 tt, 1 H, J1 = 7.8, J2 = 1.5 (H-4, pyridin ium ); 8.03 m , 2 H
Collect. Czech. Chem. Commun. 2009, Vol. 74, No. 4, pp. 643–650