Page 115 - 201812

第 12 期 甘春芳，等: 苯并咪唑基取代的甾体衍生物合成及其抗肿瘤活性 ·2083·

(9-C), 56.13 (14-C), 57.00 (17-C), 71.31 (3-C), (9-C), 56.64 (13-C), 58.60 (14-C), 71.72 (3-C),
2
2
103.99 ( J C-F = 25.2, 4-C), 105.30 ( J C-F = 22.8, 6-C), 116.26 (3-C), 121.26 (J C-F = 27.0, 6-C), 121.49 (6-C),
3
2
119.73 (9-C), 120.98 (6-C), 126.68 ( J C-F = 10.1, 7-C), 127.73 ( J C-F = 35.6, 5-C), 134.76 (7-C), 136.30 (CF 3 ),
3
1
140.40 (5-C), 142.81 ( J C-F = 11.0, 8-C), 161.40 ( J C-F 138.46 (8-C), 140.83 (5-C), 148.16 (9-C), 171.75
–1
–1
= 242.4, 5-C), 171.46 (2-C); IR (KBr), ν/cm : 3411, (2-C); IR (KBr), ν/cm : 3344, 2920, 2848, 1668, 1519,
2923, 2850, 1673, 1636, 1511, 1383, 1462, 1053, 973, 1319, 1260, 1030, 786, 729; HREIMS, m/Z: 459.2615
+
791; HREIMS, m/Z: 409.2664 [M+H] (calcd for [M+H] (calcd for C 27 H 33 F 3 N 2 O, 459.2623)。
+
C 26 H 33 FN 2 O, 409.2655)。 2-(3-羟基-17-孕甾)-5,6-二甲基苯并咪唑(6g)，
2-(3-羟基-17-孕甾)-5-甲氧基苯并咪唑 (6d)， 白色固体, 产率 92.5%, m.p. 138~141 ℃; HNMR
1
1
白色固体, 产率 94.6%，m.p. 93~95 ℃; HNMR (CDCl 3 ，300 MHz), δ: 0.80 (s, 3H, 18-CH 3 ), 1.02 (s,
(CDCl 3 , 300 MHz), δ: 0.80 (s, 3H, 18-CH 3 ), 1.02 (s, 3H, 19-CH 3 ), 2.09 (s, 3H, 5-CH 3 ), 2.25 (s, 3H, 4-CH 3 ),
3H, 19-CH 3 ), 3.50~3.55 (m, 1H, 3-αH), 3.75 (s, 1H, 3.46~3.54 (m, 1H, 3-αH), 5.35 (d, J = 4.5, 1H, 6-H),
5-OCH 3 ), 3.94 (br s, 1H, 3-OH), 5.36 (d, J = 2.4, 1H, 6.60 (d, J = 8.1, 1H, 6-H), 6.92 (d, J = 8.1, 1H, 7-H);
6-H), 6.32 (d, J = 4.5, 1H, 6-H), 6.33 (s, 1H, 3-H), 13 CNMR (75 MHz, DMSO-d 6 ), δ: 13.31 (4-CH 3 ),
13
6.85 (s, 1H, N-H), 6.97 (d, J = 4.5, 1H, 7-H); CNMR 13.37 (18-C), 19.40 (19-C), 20.52 (5-CH 3 ), 21.07
(75 MHz, DMSO-d 6 ), δ: 13.49 (18-C), 19.54 (19-C), (11-C), 23.83 (15-C), 24.59 (16-C), 31.57 (8-C),
21.20 (11-C), 23.95 (15-C), 24.72 (16-C), 29.84 31.83 (2-C), 31.97 (7-C), 36.57 (10-C), 37.33(1-C),
(8-C), 31.73(2-C), 32.09 (7-C), 36.70 (10-C), 37.42 38.63 (12-C), 42.22 (4-C), 44.15 (17-C), 50.14
(1-C), 38.83 (12-C), 42.37 (4-C), 44.28 (17-C), (9-C), 56.50 (13-C), 57.35 (14-C), 71.61 (3-C),
50.21 (9-C), 55.50 (-OCH 3 ), 56.64 (13-C), 57.49 120.52 (7-C), 121.28 (6-C), 122.21 (4-C), 122.70
(14-C), 71.84 (3-C), 103.19 (4-C), 104.87 (6-C), (6-C), 122.88 (8-C), 135.10 (9-C), 139.45 (5-C),
–1
117.63 (7-C), 121.52 (6-C), 127.00 (9-C), 140.92 140.89 (5-C), 171.87 (2-C); IR (KBr), ν/cm : 3357,
(5-C), 142.95 (8-C), 159.11 (5-C), 171.90 (2-C)；IR 2926, 2851, 1653, 1589, 1380, 1457, 1045, 956, 745;
+
–1
(KBr), ν/cm : 3369, 2922, 2853, 1656, 1629, 1514, HREIMS, m/Z: 419.3015 [M+H] (calcd for
1382, 1040, 953, 731 ； HREIMS, m/Z: 421.2851 C 28 H 38 N 2 O, 419.3062)。
+
[M+H] (calcd for C 27 H 36 N 2 O 2 , 421.2855)。 2-(3-羟基-17-孕甾)-5-甲基-6-溴苯并咪唑(6h)，
1
2-(3-羟基-17-孕甾)-5-甲基苯并咪唑(6e)，白色 白色固体 , 产率 94.0%, m.p. 92~95 ℃ ; HNMR
1
固体，产率 95.0%，m.p. 132~135 ℃；HNMR (CDCl 3 ， (CDCl 3 , 300 MHz), δ: 0.78 (s, 3H, 18-CH 3 ), 1.01 (s,
300 MHz), δ: 0.80 (s, 3H, 18-CH 3 ), 1.04 (s, 3H, 3H, 19-CH 3 ), 2.16 (s, 3H, 5-CH 3 ), 3.50~3.54 (m, 1H,
19-CH 3 ), 2.32 (s, 3H, Ph-CH 3 ), 3.49~3.59 (m, 1H, 3-αH), 3.79 ( br s, 1H, 3-OH), 5.35 (d, J = 1.6, 1H,
3-αH), 5.38 (d, J = 4.5, 1H, 6-H), 6.98 (d, J = 8.1, 1H, 6-H), 7.07 (s, 1H, 4-H), 7.10 (s, 1H, N-H), 7.22 (s, 1H,
13
6-H), 7.24 (d, J = 8.1, 1H, 7-H), 7.27 (s, 1H, 4-H),7.90 7-H); CNMR (75 MHz, DMSO-d 6 ), δ: 13.52 (18-C),
13
(s, 1H, N-H); CNMR (75 MHz, DMSO-d 6 ), δ: 13.32 17.81 (5-CH 3 ), 19.55 (19-C), 21.19 (11-C), 23.91
(18-C), 19.42 (19-C), 20.92 (Ph-CH 3 ), 21.02 (11-C), (15-C), 24.70 (16-C), 29.84 (8-C), 31.72 (2-C),
23.83 (15-C), 24.61 (16-C), 29.70 (8-C), 31.61 32.08 (7-C), 36.69 (10-C), 37.42 (1-C), 38.79
(2-C), 31.96 (7-C), 36.57 (10-C), 37.30 (1-C), 38.49 (12-C), 42.35 (4-C), 44.39 (17-C), 50.18 (9-C),
(12-C), 42.23 (4-C), 44.28 (17-C), 50.10 (9-C), 56.62 (13-C), 57.57 (14-C), 71.82 (3-C), 110.03
56.45 (13-C), 57.53 (14-C), 71.71 (3-C), 121.35 (7-C), 121.49 (6-C), 125.44 (6-C), 125.95 (4-C),
(6-C), 125.29 (7-C), 125.73 (4-C), 127.92 (6-C), 126.70 (8-C), 130.84 (5-C), 138.59 (9-C), 140.92
–1
130.75 (5-C), 136.20 (8-C), 140.47 (9-C), 140.83 (5-C), 171.96 (2-C); IR (KBr), ν/cm : 3364, 2930,
–1
(5-C), 172.21 (2-C); IR (KBr), ν/cm : 3421, 2930, 2850, 1651, 1467, 1374, 1048, 901, 729; HREIMS,
+
2848, 1663, 1516, 1043, 811, 734, 594; HREIMS, m/Z: m/Z: 483.2005 [M+H] (calcd for C 27 H 35 BrN 2 O,
+
405.2903 [M+H] (calcd for C 27 H 36 N 2 O, 405.2906)。 483.2011)。
2-(3- 羟基 -17- 孕甾 )-5- 三氟甲基苯并咪唑 2-(3-羟基-17-孕甾)-6,7-二甲基苯并咪唑(6i)，
1
(6f)，白色固体，产率 89.6%，m.p. 140~143 ℃； 白色固体，产率 89.0%, m.p. 114~116 ℃; HNMR
1 (CDCl 3 ，300 MHz), δ: 0.82 (s, 3H, 18-CH 3 ), 1.04 (s,
HNMR (CDCl 3 ，300 MHz), δ: 0.81 (s, 3H, 18-CH 3 ),
1.02 (s, 3H, 19-CH 3 ), 3.48~3.61 (m, 1H, 3-αH), 5.31 3H, 19-CH 3 ), 2.15 (s, 3H, 5-CH 3 ), 2.18 (s, 3H, 6-CH 3 ),
(s, 1H, -OH), 5.39 (d, J = 5.1, 1H, 6-H), 7.54 (d, J = 3.49~3.60(m, 1H, 3-αH), 5.38 (d, J = 4.5, 1H, 6-H),
8.4, 1H, 7-H), 8.18 (d, J = 8.4, 1H, 6-H), 8.83 (s, 1H, 6.62 (s, 1H, 4-H), 6.95 (s, 1H, 7-H), 6.97 (s, 1H, N-H);
4-H), 9.80 (s, 1H, N-H); 13 CNMR (75 MHz, 13 CNMR (75 MHz, DMSO-d 6 ), δ: 13.31 (18-C), 18.76
DMSO-d 6 ), δ: 13.17 (18-C), 19.41 (19-C), 21.08 (6-CH 3 ), 19.33 (5-CH 3 ), 19.41 (19-CH 3 ), 21.07
(11-C), 23.44 (15-C), 24.62 (16-C), 29.69 (8-C), (11-C), 23.81 (15-C), 24.58 (16-C), 31.61 (8-C),
31.86 (2-C), 32.02 (7-C), 36.57 (10-C), 37.29 (1-C), 31.82 (2-C), 31.97 (7-C), 36.57 (10-C), 37.30 (1-C),
38.33 (12-C), 42.27 (4-C), 44.24 (17-C), 50.17 38.66 (12-C), 42.25 (4-C), 44.14 (13-C), 50.11