STE 7704
No. of Pages 7, Model 5G
10 January 2015
J. Cui et al. / Steroids xxx (2015) xxx–xxx
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4.1.2.2. Dehydroepiandrosterone pyridine-3-methanylidenehydrazone
157.6 (22-C), 158.7 (20-ArAC), 183.0 (17-C); HRESI-MS (m/z):
(4). Faint yellow crystals, yield: 74%, m.p.: 195–197 °C; IR (KBr)
m/
471.3015 [M+H]+ (calcd for C31H39N2O2, 471.3012).
cmꢀ1: 3399, 3277, 2958, 2921, 2843, 1732, 1646, 1418, 1364, 1324,
1258, 1058, 1037, 964, 800; 1H NMR (300 MHz, CDCl3) d: 1.00 (3H,
s, 18-CH3), 1.06 (3H, s, 19-CH3), 2.67–2.61 (2H, m, C16-H), 3.59–
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4.1.2.6. Dehydroepiandrosterone quinoline-4-methanylidenehydraz-
one (8). White crystals, yield: 95%, m.p.: 207–208 °C; IR (KBr) m/
3.49 (1H, m, C3AaH), 5.38 (1H, d, J = 5.1, C6AH), 7.35 (1H, dd,
cmꢀ1: 3350, 2933, 2852, 1646, 1573, 1507, 1462, 1368, 1062,
764; 1H NMR (300 MHz, CDCl3) d: 1.05 (3H, s, 18-CH3), 1.07 (3H,
s, 19-CH3), 2.76–2.69 (2H, m, C16AH), 3.61–3.51 (1H, m,
J = 7.8, 4.8, 50-ArAH), 8.12 (1H, d, d, J = 7.8, 40-ArAH), 8.31 (1H, s,
C22AH), 8.63 (1H, dd, J = 4.8, 1.2, 60-ArAH), 8.88 (1H, d, J = 1.2,
20-ArAH); 13C NMR (75 MHz, CDCl3) d: 16.5 (19-C), 19.5 (18-C),
20.7 (11-C), 23.3 (15-C), 28.0 (16-C), 31.3 (8-C), 31.5 (2-C), 31.6
(7-C), 33.8 (12-C), 36.7 (1-C), 37.2 (10-C), 42.3 (13-C), 44.4 (4-C),
50.3 (9-C), 53.6 (14-C), 71.5 (3-C), 121.0 (6-C), 123.7 (50-ArAC),
130.5 (40-ArAC), 134.5 (30-ArAC), 141.1 (5-C), 149.8 (20-ArAC),
151.2 (22-C), 154.3 (60-ArAC), 183.8 (17-C); HRESI-MS (m/z):
392.2719 [M+H]+ (calcd for C25H34N3O, 392.2702).
C3Aa
H), 5.38 (1H, d, J = 4.8, C6AH), 7.64 (1H, t, J = 7.5, 70-ArAH),
7.76 (1H, d, J = 7.5, 60-ArAH), 7.78 (1H, d, J = 4.8, 30-ArAH), 8.18
(1H, d, J = 8.1, 80-ArAH), 8.74 (1H, d, J = 8.1, 50-ArAH), 8.91 (1H, s,
C22AH), 8.98 (1H, d, J = 4.8, 20-ArAH); 13C NMR (75 MHz, CDCl3)
d: 16.5 (19-C), 19.5 (18-C), 20.7 (11-C), 23.4 (15-C), 28.5 (16-C),
31.3 (8-C), 31.5 (2-C), 31.6 (7-C), 33.8 (12-C), 36.7 (1-C), 37.3
(10-C), 42.3 (13-C), 44.6 (4-C), 50.3 (9-C), 53.6 (14-C), 71.6 (3-C),
120.9 (30-ArAC), 121.0 (6-C), 124.5 (90-ArAC), 125.7 (50-ArAC),
127.6 (60-ArAC), 129.5 (70-ArAC), 130.1 (80-ArAC), 137.9
(100-ArAC), 141.1 (40-ArAC), 148.9 (5-C), 150.1 (20-ArAC), 155.0
(22-C), 184.6 (17-C); HRESI-MS (m/z): 442.2859 [M+H]+ (calcd for
C29H36N3O, 442.2858).
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4.1.2.3. Dehydroepiandrosterone thiophene-3-methanylidenehydraz-
one (5). Faint yellow crystals, yield: 80%, m.p.: 195–196 °C; IR
(KBr) m
/cmꢀ1: 3428, 2933, 2897, 2852, 1728, 1642, 1446, 1364,
1238, 1057; 1H NMR (300 MHz, CDCl3) d: 0.97 (3H, s, 18-CH3),
1.04 (3H, s, 19-CH3), 2.65–2.58 (2H, m, C16-H), 3.56–3.46 (1H, m,
C3Aa
H), 5.35 (1H, d, J = 4.8, C6AH), 7.31 (1H, dd, J = 4.8, 2.7, 40-
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4.1.2.7. Dehydroepiandrosterone 3-hydroxybenzylidenehydrazone
ArAH), 7.54 (1H, d, J = 4.8, 50-ArAH), 7.59 (1H, d, J = 2.7, 20-ArAH),
8.30 (1H, s, C22AH); 13C NMR (75 MHz, CDCl3) d: 16.5 (19-C), 19.5
(18-C), 20.7 (11-C), 23.3 (15-C), 27.9 (16-C), 31.3 (8-C), 31.5 (2-C),
31.6 (7-C), 33.9 (12-C), 36.7 (1-C), 37.2 (10-C), 42.2 (13-C), 44.3
(4-C), 50.4 (9-C), 53.6 (14-C), 71.5 (3-C), 121.0 (6-C), 125.6
(40-ArAC), 126.5 (50-ArAC), 128.4 (20-ArAC), 138.1 (5-C), 141.1
(30-ArAC), 152.1 (22-C), 182.8 (17-C); HRESI-MS (m/z): 397.2332
[M+H]+ (calcd for C24H33N2OS, 397.2314).
(9). White solids, yield: 51%, m.p.: 136–138 °C; IR (KBr) m :
/cmꢀ1
3419, 2929, 2851, 2357, 2340, 1723, 1654, 1450, 1380, 1258,
1217; 1H NMR (300 MHz, CDCl3) d: 0.91 (3H, s, 18-CH3), 0.99
(3H, s, 19-CH3), 2.60–2.43 (2H, m, C16AH), 3.40–3.25 (1H, m, C3-
a
H), 4.62 (1H, s, AOH), 5.30 (1H, d, J = 4.5, C6AH), 6.87–6.84 (1H,
m, 20-ArAH), 7.30–7.15 (3H, m, 40,50,60-ArAH), 8.21 (1H, s,
C22AH), 9.62 (1H, s, ArAOH); 13C NMR (75 MHz, DMSO) d: 16.9
(19-C), 19.7 (18-C), 20.8 (11-C), 23.4 (15-C), 27.9 (16-C), 31.2 (8-
C), 31.5 (2-C), 31.9 (7-C), 34.2 (12-C), 36.7 (1-C), 37.4 (10-C), 42.7
(13-C), 44.4 (4-C), 50.4 (9-C), 53.4 (14-C), 70.4 (3-C), 114.0 (60-
ArAC), 118.3 (6-C), 119.8 (40-ArAC), 120.6 (20-6-C), 130.2 (50-
ArAC),136.1 (30-ArAC), 141.9 (5-C), 157.4 (22-C), 158.0 (10-ArAC),
181.8 (17-C); HRESI-MS (m/z): 407.2697 [M+H]+ (calcd for
C26H35N2O2, 407.2699).
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4.1.2.4. Dehydroepiandrosterone naphthalen-2-methanylidenehydraz-
one (6). White crystals, yield: 95%, m.p.: 110–111 °C; IR (KBr) m/
cmꢀ1: 3387, 2929, 2896, 2855, 2831, 1732, 1646, 1576, 1511,
1454, 1429, 1372, 1331, 1061, 800, 767; 1H NMR (300 MHz, CDCl3)
d: 1.05 (3H, s, 18-CH3), 1.06 (3H, s, 19-CH3), 2.83–2.70 (2H, m,
C16AH), 3.57–3.47 (1H, m, C3AaH), 5.37 (1H, d, J = 3.6, C6AH),
7.63–7.49 (3H, m, ArAH), 7.96–7.87 (3H, m, ArAH), 8.95 (1H, s,
10-ArAH), 8.98 (1H, s, C22-H); 13C NMR (75 MHz, CDCl3) d: 16.6
(19-C), 19.5 (18-C), 20.7 (11-C), 23.4 (15-C), 28.5 (16-C), 31.4
(8-C), 31.5 (2-C), 31.6 (7-C), 34.0 (12-C), 36.7 (1-C), 37.3 (10-C),
42.3 (13-C), 44.4 (4-C), 50.4 (9-C), 53.7 (14-C), 71.5 (3-C), 121.0
(6-C), 125.0 (90-ArAC), 125.3 (70-ArAC), 126.1 (30-ArAC), 127.2
(10-ArAC), 128.7 (40-ArAC), 129.3 (50-ArAC), 130.2 (60-ArAC),
131.2 (80-ArAC), 131.3 (20-ArAC), 133.9 (100-ArAC), 141.1 (5-C),
157.9 (22-C), 183.4 (17-C); HRESI-MS (m/z): 441.2930 [M+H]+
(calcd for C30H37N2O, 441.2906).
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4.1.2.8. Dehydroepiandrosterone indol-3-methanylidenehydrazone
(10). White crystals, yield: 72%, m.p.: 234–236 °C; IR (KBr)
m/
cmꢀ1: 3395, 3224, 2929, 2851, 2823, 2361, 1654, 1589, 1568,
1527, 1450, 1388, 1241, 1053; 1H NMR (300 MHz, CDCl3)d: 1.03
(3H, s, 18-CH3), 1.08 (3H, s, 19-CH3), 2.90–2.80 (2H, m, C16AH),
3.62–3.51 (1H, m, C3AaH), 5.41 (1H, d, J = 4.8, C6AH), 7.32–7.26
(1H, m, 60-ArAH), 7.41 (1H, dd, J = 6.3, 3.0, 50-ArAH), 7.49 (1H, d,
J = 2.7, 70-ArAH), 8.39–8.38 (1H, m, 40-ArAH), 8.65 (1H, s,
C22AH), 8.80 (1H, s, ANH); 13C NMR (75 MHz, CDCl3) d: 16.6
(19-C), 19.5 (18-C), 20.8 (11-C), 23.4 (15-C), 28.3 (16-C), 31.4 (8-
C), 31.5 (2-C), 31.6 (7-C), 34.1 (12-C), 36.6 (1-C), 37.2 (10-C), 42.3
(13-C), 44.1 (4-C), 50.4 (9-C), 53.8 (14-C), 71.7 (3-C), 111.2 (70-
ArAC), 114.0 (30-ArAC), 121.2 (6-C), 121.5 (50-ArAC), 122.8 (60-
ArAC), 123.5 (40-ArAC), 125.1 (80-ArAC), 129.3 (20-ArAC), 136.9
(90-ArAC), 141.0 (5-C), 153.7 (22-C), 182.5 (17-C); HRESI-MS (m/
z): 430.2889 [M+H]+ (calcd for C28H36N3O, 430.2858).
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4.1.2.5. Dehydroepiandrosterone 6-methoxynaphthalen-2-metha-
nylidenehydrazone (7). White crystals, yield: 77%, m.p.: 100–
101 °C; IR (KBr)
m
/cmꢀ1: 3423, 2929, 2829, 1621, 1593, 1474,
1380, 1331, 1262, 1241, 1196, 1164, 1053, 1021, 857; 1H NMR
(300 MHz, CDCl3) d: 1.01 (3H, s, 18-CH3), 1.05 (3H, s, 19-CH3),
2.72–2.67 (2H, m, C16AH), 3.57–3.49 (1H, m, C3AaH), 3.914 (3H,
s, ArAOACH3), 5.36 (1H, d, J = 3.9, C6AH), 7.14 (1H, s, 10-ArAH),
7.16 (1H, d, J = 8.4, ArAH), 7.74 (1H, d, J = 9.3, 80-ArAH), 7.77 (1H,
d, J = 9.3, 70-ArAH), 7.96 (1H, s, 50-ArAH), 8.00 (1H, d, J = 8.4, 40-
ArAH), 8.43 (1H, s, C22-H); 13C NMR (75 MHz, CDCl3) d: 16.7
(19-C), 19.5 (18-C), 20.7 (11-C), 23.4 (15-C), 28.1 (16-C), 31.3
(8-C), 31.5 (2-C), 31.6 (7-C), 33.9 (12-C), 36.7 (1-C), 37.2 (10-C),
42.3 (13-C), 44.3 (4-C), 50.4 (9-C), 53.6 (14-C), 55.4 (ArAOAC),
71.5 (3-C), 106.1 (10-ArAC), 119.2 (30-ArAC), 121.1 (90-ArAC),
124.3 (6-C), 127.3 (80-ArAC), 128.5 (70-ArAC), 129.8 (50-ArAC),
130.1 (40-ArAC), 130.3 (60-ArAC), 136.0 (100-ArAC), 141.1 (5-C),
4.1.2.9.
Dehydroepiandrosterone
propan-2-ylidenehydrazone
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(11). White crystals, yield: 81%, m.p.: 171–172 °C; IR (KBr)
m/
cmꢀ1: 3427, 2929, 2888, 2855, 1662, 1450, 1425, 1368, 1241,
1053, 1033, 851, 800, 735; 1H NMR (300 MHz, CDCl3)d: 0.92 (3H,
s, 18-CH3), 1.02 (3H, s, 19-CH3), 1.81 (3H, s, 23-CH3), 1.98 (3H, s,
24-CH3), 3.53–3.43 (1H, m, C3AaH), 5.34 (1H, d, J = 4.8, C6AH);
13C NMR (75 MHz, CDCl3) d: 16.6 (19-C), 17.6 (18-C), 19.5 (24-C),
20.7 (11-C), 23.3 (23-C), 25.0 (15-C), 27.1 (16-C), 31.3 (8-C), 31.5
(2-C), 31.6 (7-C), 34.0 (12-C), 36.6 (1-C), 37.3 (10-C), 42.2 (13-C),
44.1 (4-C), 50.5 (9-C), 53.7 (14-C), 71.4 (3-C), 121.0 (6-C), 141.2
Please cite this article in press as: Cui J et al. Synthesis, characterization and antitumor activities of some steroidal derivatives with side chain of 17-hydra-
Q1