254
steroids 7 3 ( 2 0 0 8 ) 252–256
3.5, 11.0, C3-␣H), 6.243 (s, 1H, C4-H); 13C NMR(CDCl3, 125 MHz):
35.2 (1-C), 29.7 (2-C), 69.1 (3-C), 113.8 (4-C), 156.7 (5-C), 156.9 (6-
C), 28.1 (7-C), 33.9 (8-C), 53.6 (9-C), 41.7 (10-C), 21.4 (11-C), 39.7
(12-C), 42.5 (13-C), 56.1 (14-C), 23.1 (15-C), 26.2 (16-C), 55.8 (17-
C), 11.9 (18-C), 19.8 (19-C), 36.1 (20-C), 18.7 (21-C), 34.2 (22-C),
24.1 (23-C), 45.9 (24-C), 29.2 (25-C), 18.4 (26-C), 19.0 (27-C), 24.2
(28-C), 12.0 (29-C).
2.1.10. (6E)-Hydroximino-24-ethylcholest-4-en-3-one (1)
The Jones’ reagent of 0.5 mL (0.267 mol/L) was added drop-
wise to the solution of 8a (73 mg, 0.164 mmol) in 10 mL of
acetone in 10 min. The reaction mixture was stirred at room
temperature for 1 h and then neutralized with 10% K2CO3
solution. The suspension was poured over a silica gel col-
umn and eluted with ethyl acetate. The solvent was removed
under reduced pressure. The residue was chromatographed
on silica gel using petroleum ether (60–90 ◦C)/EtOAc (3:1) as
eluent to give 46 mg (63%) of 1, ꢀm.p. 197–198 ◦C; IR(KBr) ꢁ: 3383,
In the reaction, the 6Z-isomer 9a of 8a was obtained in 3%
yield, ꢀm.p. 119–121 ◦C; IR(KBr) ꢁ: 3412, 2958, 2938, 2872, 1630,
;
1462, 1377, 1123, 911 cm−1 1H NMR(CDCl3, 500 MHz): 0.719 (s,
2958, 2933, 2868, 1704, 1659, 1585, 1462, 1377, 1250, 984 cm−1
;
3H, 18-CH3), 0.839 (d, 3H, J = 7.0, 26-CH3 or 27-CH3), 0.861 (d,
3H, J = 7.0, 26-CH3 or 27-CH3), 0.869 (t, 3H, J = 8.0, 29-CH3), 0.937
(d, 3H, J = 6.0, 21-CH3), 1.109 (s, 3H, 19-CH3), 2.333-2.370 (m, 2H,
1H NMR(CDCl3, 500 MHz): 0.737 (s, 3H, 18-CH3), 0.839 (d, 3H,
J = 6.5, 26-CH3 or 27-CH3), 0.861 (d, 3H, J = 6.5, 26-CH3 or 27-
CH3), 0.868 (t, 3H, J = 8.5, 29-CH3), 0.956 (d, 3H, J = 6.5, 21-CH3),
1.064 (s, 3H, 19-CH3), 2.274 (ddd, 1H, J = 5.0, 14.0, 18.5, C7-
␣H), 2.662 (dd, 1H, J = 4.0, 16.5, C2–H), 3.097 (dd, 1H, J = 3.5,
18.5, C7-H), 6.778 (s, 1H, C4-H), 8.917 (brs, 1H, N-OH); 13C
NMR(CDCl3, 125 MHz): 36.1 (1-C), 33.4 (2-C), 200.9 (3-C), 126.3
(4-C), 155.8 (5-C), 149.2 (6-C), 26.0 (7-C), 33.4 (8-C), 50.0 (9-C),
42.5 (10-C), 21.3 (11-C), 39.3 (12-C), 46.0 (13-C), 56.7 (14-C), 24.0
(15-C), 28.0 (16-C), 55.9 (17-C), 11.9 (18-C), 18.9 (19-C), 38.9 (20-
C), 18.7 (21-C), 33.9 (22-C), 26.1 (23-C), 45.9 (24-C), 29.2 (25-C),
19.8 (26-C), 19.0 (27-C), 23.1 (28-C), 12.0 (29-C); LREIMS (70 eV,
m/z %): 441 (M+, 26), 426 (M+-CH3, 100), 424 (M+-OH, 35), 152
(38), 127 (89); HREIMS: m/z 441.3604 [M]+ (calcd for C29H47O2N1,
441.3601).
C7-H), 4.322 (dd, 1H, J = 4.5, 12.0, C3-␣H), 6.922 (s, 1H, C4-H); 13
C
NMR(CDCl3, 125 MHz): 36.1 (1-C), 29.2 (2-C), 69.3 (3-C), 113.9 (4-
C), 153.7 (5-C), 160.5 (6-C), 29.7 (7-C), 33.9 (8-C), 53.8 (9-C), 39.6
(10-C), 21.2 (11-C), 39.4 (12-C), 42.0 (13-C), 56.0 (14-C), 24.2 (15-
C), 26.2 (16-C), 55.7 (17-C), 11.9 (18-C), 19.8 (19-C), 36.8 (20-C),
18.7 (21-C), 34.3 (22-C), 24.5 (23-C), 45.9 (24-C), 28.1 (25-C), 19.0
(26-C), 18.9 (27-C), 23.1 (28-C), 12.0 (29-C).
2.1.8. (6E)-Hydroximinocholest-4-en-3ˇ-ol (8b)
Yield 74.5%,
155–157 ◦C; IR(KBr) ꢁ: 3374, 2949, 2864, 1629,
m.p.
1462, 1376, 1315, 1119, 1070, 968, 890, 727, 674 cm−1 1H
;
NMR(CDCl3, 500 MHz): 0.717 (s, 3H, 18-CH3), 0.882 (d, 3H, J = 2.0,
26-CH3 or 27-CH3), 0.895 (d, 3H, J = 2.0, 26-CH3 or 27-CH3), 0.931
(d, 3H, J = 6.5, 21-CH3), 1.070 (s, 3H, 19-CH3), 3.059 (dd, 1H, J = 3.0,
14.0, C7-H), 4.273 (dd, 1H, J = 4.4, 12.0 Hz, C3-␣H), 6.249 (s, 1H,
C4-H).
In the reaction, the 6Z-isomer 9b of 8b was obtained in
4% yield, ꢀm.p. 124–126 ◦C; IR(KBr) ꢁ: 3411, 2958, 2872, 1629,
1462, 1376 cm−1 1H NMR(CDCl3, 500 MHz): 0.762 (s, 3H, 18-
;
2.1.11. (6E)-Hydroximinocholest-4-en-3-one (2)
Yield 61%, ꢀm.p. 188–191 ◦C; IR(KBr) ꢁ: 3738, 3281, 2942, 2868,
1716, 1659, 1581, 1471, 1381, 1250, 1283, 1172, 1127, 1078, 1029,
980, 927, 866, 788, 735 cm−1 1H NMR(CDCl3, 500 MHz): 0.734
;
(s, 3H, 18-CH3), 0.884 (d, 3H, J = 6.2, 26-CH3 or 27-CH3), 0.897
(d, 3H, J = 6.2, 26-CH3 or 27-CH3), 0.942 (d, 3H, J = 6.5, 21-CH3),
1.159 (s, 3H, 19-CH3), 2.274 (ddd, 1H, J = 5.0, 14.0, 18.5, C7-␣H),
2.519 (dd, 1H, J = 5.1, 14.7, C2-H), 3.437 (dd, 1H, J = 4.6, 15.9, C7-
H), 6.338 (s, 1H, C4-H), 9.033 (brs, 1H, N-OH); 13C NMR(CDCl3,
125 MHz): 36.1 (1-C), 33.5 (2-C), 200.9 (3-C), 126.3 (4-C), 155.7 (5-
C), 149.2 (6-C), 28.0 (7-C), 33.3 (8-C), 50.0 (9-C), 42.5 (10-C), 21.3
(11-C), 39.5 (12-C), 46.0 (13-C), 56.7 (14-C), 24.0 (15-C), 28.1 (16-
C), 56.0 (17-C), 11.9 (18-C), 18.9 (19-C), 35.7 (20-C), 18.7 (21-C),
38.9 (22-C), 23.8 (23-C), 39.3 (24-C), 28.0 (25-C), 22.8 (26-C), 22.5
(27-C); LREIMS (70 eV, m/z %): 413 (M+, 79), 396 (M+-OH, 100),
395 (M+-H2O, 30), 152(93); HREIMS: m/z 413.3289 [M]+ (calcd for
C27H43O2N1, 413.3288).
CH3), 0.894 (d, 3H, J = 2.3, 26 or 27-CH3), 0.902 (d, 3H, J = 2.3, 26
or 27-CH3), 0.965 (d, 3H, J = 6.5, 21-CH3), 1.144 (s, 3H, 19-CH3),
4.277 (m, 1H, C3-␣H), 6.937 (d, 1H, J = 2.1, C4-H).
2.1.9. (6E)-Hydroximino-24-ethylcholest-4,22-dien-3ˇ-ol
(8c)
Yield 69.1%, ꢀm.p. 96–97 ◦C; IR(KBr) ꢁ: 3399, 2954, 2929, 2868,
1634, 1462, 1381, 1074, 968 cm−1 1H NMR(CDCl3, 500 MHz):
;
0.739 (s, 3H, 18-CH3), 0.822 (d, 3H, J = 7.7, 26-CH3 or 27-CH3),
0.872 (d, 3H, J = 7.0, 26-CH3 or 27-CH3), 0.829 (t, 3H, J = 7.5, 29-
CH3), 1.040 (d, 3H, J = 6.0, 21-CH3), 1.078 (s, 3H, 19-CH3), 3.064
(dt, 1H, J = 3.5, 17.5, C7-H), 4.282 (ddd, 1H, J = 2.0, 5.5, 12.5, C3-
␣H), 5.049 (dd, 1H, J = 9.0, 15.0, C22-H), 5.172 (dd, 1H, J = 8.5, 15.0,
C23-H), 6.247 (s, 1H, C4-H); 13C NMR(CDCl3, 125 MHz): 35.2 (1-C),
29.7 (2-C), 69.0 (3-C), 113.9 (4-C), 156.7 (5-C), 156.9 (6-C), 28.8 (7-
C), 31.9 (8-C), 51.2 (9-C), 39.5 (10-C), 21.2 (11-C), 38.5 (12-C), 40.4
(13-C), 55.9 (14-C), 21.4 (15-C), 25.4 (16-C), 53.6 (17-C), 12.2 (18-
C), 18.7 (19-C), 41.6 (20-C), 19.0 (21-C), 138.1 (22-C), 129.5 (23-C),
42.4 (24-C), 34.2 (25-C), 21.1 (26-C), 18.4 (27-C), 24.3 (28-C), 12.1
(29-C).
In the reaction, the 6Z-isomer 9c of 8c was obtained in 3.5%
yield, ꢀm.p. 125–127 ◦C; IR(KBr): 3420, 2958, 2868, 1638, 1462,
1381, 1025, 976 cm−1 1H NMR(CDCl3, 500 MHz): 0.736 (s, 3H,
;
18-CH3), 0.820 (d, 3H, J = 6.0, 26-CH3 or 27-CH3), 0.826 (t, 3H,
J = 8.0, 29-CH3), 0.870 (d, 3H, J = 6.0, 26-CH3 or 27-CH3), 1.036 (d,
3H, J = 6.5, 21-CH3), 1.110 (s, 3H, 19-CH3), 4.323 (dd, 1H, J = 4.0,
11.5, C3-␣H), 5.047 (dd, 1H, J = 9.0, 14.5, C22-H), 5.168 (dd, 1H,
J = 8.5, 14.5, C23-H), 6.922 (s, 1H, C4-H).
2.1.12. (6E)-Hydroximino-24-ethylcholest-4,22-dien-3-one
(4)
Yield 60%, ꢀm.p. 185–187 ◦C; IR(KBr) ꢁ: 3371, 2958, 2868,
1708, 1679, 1581, 1458, 1377, 1242, 976 cm−1 1H NMR(CDCl3,
;
500 MHz): 0.759 (s, 3H, 18-CH3), 0.833 (t, 3H, J = 7.5, 29-CH3),
0.826 (d, 3H, J = 6.5, 26-CH3 or 27-CH3), 0.875 (d, 3H, J = 6.5,
26-CH3 or 27-CH3), 1.061 (d, 3H, J = 8.5, 21-CH3), 1.069 (s, 3H,
19-CH3), 2.274 (ddd, 1H, J = 5.5, 14.5, 18.0, C7-␣H), 2.657 (dd, 1H,
J = 3.0, 16.0, C2-H), 3.097 (dd, 1H, J = 5.0, 18.0, C7-H), 5.065 (dd,
1H, J = 9.0, 15.5, C22-H), 5.181 (dd, 1H, J = 8.5, 15.5, C23-H), 6.779
(s, 1H, C4-H); 13C NMR(CDCl3, 125 MHz) ı: 38.9 (1-C), 33.5 (2-C),
200.9 (3-C), 126.3 (4-C), 155.8 (5-C), 149.1 (6-C), 28.7 (7-C), 31.9
(8-C), 51.3 (9-C), 42.4 (10-C), 21.3 (11-C), 39.2 (12-C), 46.0 (13-C),
56.8 (14-C), 24.1 (15-C), 31.8 (16-C), 55.9 (17-C), 12.2 (18-C), 18.9
(19-C), 40.4 (20-C), 21.1 (21-C), 137.9 (22-C), 129.7 (23-C), 50.1