Page 113 - 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 ·2081·

124.80、125.20、126.90、139.70 (苯并咪唑-C), 140.80 (1-C), 37.16 (10-C), 38.19 (4-C), 38.75 (12-C),
(5-C), 170.60 (2-C), 171.60 (3-OCOCH 3 ); IR (KBr), 44.27 (17-C), 50.12 (9-C), 56.6 (13-C), 57.42
–1
ν/cm : 3345, 2938, 2847, 1730, 1649, 1627, 1375, (14-C), 74.01 (3-C), 103.15 (4-C), 104.83 (6-C),
+
1251, 1030, 743; HREIMS, m/Z: 433.2843 [M+H] 117.65 (7-C), 122.47 (6-C), 127.03 (9-C), 139.81
(calcd for C 28H 37N 2O 2, 433.2855)。 (5-C), 142.97 (8-C), 159.10 (5-C), 170.80 (2-C),
–1
171.94 (3-OCOCH 3 ); IR (KBr), ν/cm : 3413, 2930,
2-(3-乙酰氧基-17-孕甾)-5-氯苯并咪唑 (5b)， 2857, 1716, 1621, 1516, 1030, 966, 843, 791;
1
淡黄色固体, 产率 34.7%，m.p. 98~100 ℃; HNMR HREIMS, m/Z: 463.2954 [M+H] (calcd for C 29H 39N 2O 3,
+
(CDCl 3 , 300 MHz), δ: 0.82 (s, 3H, 18-CH 3 ), 1.05 (s, 463.2961)。
3H, 19-CH 3 ), 2.05 (s, 3H, 3-OCOCH 3 ), 4.58~4.68 (m, 2-(3- 乙酰 氧基 -17- 孕甾 )-5- 甲基 苯并咪唑
1H, 3-H), 5.40 (d, J =4.50, 1H, 6-H), 6.76 (dd, J =
8.4, 2.1, 1H, 6-H), 6.81 (d, J = 2.1, 1H, 4-H), 6.98 (s, (5e)，白色固体, 产率 52.6%，m.p. 132~134 ℃;
1
1H, N-H), 7.10 (d, J = 8.4, 1H, 7-H); 13 CNMR HNMR (CDCl 3 , 300 MHz), δ: 0.80 (s, 3H, 18-CH 3 ),
(75 MHz, DMSO-d 6 ), δ: 13.33 (18-C), 19.30 (19-C), 1.04 (s, 3H, 19-CH 3 ), 2.03 (s, 3H, 3-OCOCH 3 ), 2.25
21.00 (11-C), 21.40 (3-CH 3 CO), 23.82 (15-C), 24.55 (s, 3H, 5-CH 3 ), 4.53~4.70 (m, 1H, 3-αH), 5.40 (d, J
(16-C), 27.73 (2-C), 29.69 (8-C), 31.93 (7-C), 36.66 =3.6, 1H, 6-H), 6.58 (d, J =7.8, 1H, 6-H), 7.00 (d, J
13
(1-C), 37.04 (10-C), 38.07 (4-C), 38.67 (12-C), =7.8, 1H, 7-H), 7.20 (s, 1H, 4-H); CNMR (75 MHz,
44.21 (17-C), 50.00 (9-C), 56.46 (13-C), 57.51 DMSO-d 6), δ: 13.32 (18-C), 19.30 (19-C), 20.45
(14-C), 73.84 (3-C), 117.76 (4-C), 119.21 (7-C), (5-CH 3 ), 21.00 (3-CH 3 CO), 21.40 (11-C), 23.84
122.27 (6-C), 123.16 (6-C), 126.26 (5-C), 132.13 (15-C), 24.59 (16-C), 27.73 (2-C), 31.82 (8-C),
(9-C), 139.71 (8-C), 142.12 (5-C), 170.59 (2-C), 31.92 (7-C), 36.66 (1-C), 37.06 (10-C), 38.07 (4-C),
–1
171.66 (3-OCOCH 3 ); IR(KBr), ν/cm : 3343, 2933, 38.52 (12-C), 44.15 (17-C), 50.03 (9-C), 56.42
2849, 1730, 1663, 1373, 1246, 1035, 803; HREIMS, (13-C), 57.29 (14-C), 73.91 (3-C),118.63 (7-C),
+
m/Z: 467.2460 [M+H] (calcd for C 38 H 36ClN 2O 2, 120.05 (4-C), 122.06 (6-C), 122.33 (6-C), 125.31
467.2456)。 (5-C), 136.89 (8-C), 139.71 (9-C), 140.93 (5-C),
–1
170.65 (2-C), 171.61 (3-OCOCH 3 ); IR (KBr), ν/cm :
2-(3-乙酰氧基-17-孕甾)-5-氟苯并咪唑(5c)，淡 3339, 2925, 2850, 1733, 1654, 1369, 1260, 1030,794;
1
+
黄色固体, 产率 53.6%，m.p.123~125 ℃; HNMR HREIMS, m/Z: 447.3039 [M+H] (calcd for
(CDCl 3 ，300 MHz), δ: 0.80 (s, 3H，18-CH 3 ), 1.05 (s, C 29 H 39 N 2 O 2 , 447.3012)。
3H, 19-CH 3 ), 2.03 (s, 3H, 3-OCOCH 3 ), 4.56~4.67 (m, 2-(3-乙酰氧基-17-孕甾)-5-三氟甲基苯并咪唑
1H, 3-αH), 5.40 (d, J = 4.50, 1H, 6-H), 6.50~6.41 (m, (5f)，白色固体, 产率 53.2%，m.p. 112~115 ℃;
1H, 6-H), 7.05~ 7.01 (m, 1H, 7-H), 7.17 (d, J F-H = 14.4, 1 HNMR (CDCl 3 ，300 MHz), δ: 0.82 (s, 3H, 18-CH 3 ),
1H, 4-H); 13 CNMR (75 MHz, DMSO-d 6 ), δ: 13.37
(18-C), 19.29 (19-C), 21.01 (11-C), 21.39 1.06 (s, 3H, 19-CH 3 ), 2.03 (s, 3H, 3-OCOCH 3 ),
4.58~4.68 (m, 1H, 3-αH), 5.41 (d, J = 4.8, 1H, 6-H),
(3-CH 3 CO), 23.85 (15-C), 24.57 (16-C), 27.72 6.83 (d, J = 8.4, 1H, 7-H), 7.33 (d, J = 8.4, 1H, 6-H),
(2-C), 31.79 (8-C), 31.92 (7-C), 36.66 (1-C), 37.07 7.40 (s, 1H, 4-H); CNMR (75 MHz, DMSO-d 6 ), δ:
13
(10-C), 38.06 (4-C), 38.60 (12-C), 44.19 (17-C), 13.39 (18-C), 19.28 (19-C), 21.01 (11-C), 21.36
50.02 (9-C), 56.44 (13-C), 57.23 (14-C), 73.91 (3-C), (3-CH 3 CO), 23.87 (15-C), 24.57 (16-C), 27.70
2
2
104.20 ( J C-F = 25.1, 4-C), 105.47 ( J C-F = 22.7, 6-C), (2-C), 31.79 (8-C), 31.94 (7-C), 36.68 (1-C), 37.08
3
122.30 (6-C), 127.14 ( J C-F = 9.9, 7-C), 129.02 (9-C), (10-C), 38.05 (4-C), 38.62 (12-C), 44.30 (17-C),
3
139.70 (5-C), 143.29 ( J C-F = 43.8, 8-C), 161.77 (J C-F 50.00 (9-C), 56.47 (13-C), 57.35 (14-C), 73.95 (3-C),
= 242.0, 5-C), 170.69 (2-C), 171.90 (3-OCOCH 3 ); IR 117.51 (4-C), 120.73 (7-C), 122.28 (6-C), 122.57
–1
(KBr), ν/cm : 3350, 2938, 2844, 1718, 1375, 1658, (5-CF 3), 122.88 (6-C), 123.88 (5-C), 126.16 (8-C),
1605, 1251,1028, 841; HREIMS, m/Z: 451.2766 139.73 (5-C), 144.44 (9-C), 170.80 (2-C), 171.95
+
[M+H] (calcd for C 28 H 36 FN 2 O 2 , 451.2761)。 (C==O); IR (KBr), ν/cm : 3351, 2937, 2903, 1716,
–1
2-(3-乙酰氧基-17-孕甾)-5-甲氧基苯并咪唑 1324, 1110, 1075, 891, 624; HREIMS, m/Z: 501.2713
+
1
(5d)，白色固体, 产率 60.53%，m.p. 96~98 ℃; H [M+H] (calcd for C 29 H 36 F 3 N 2 O 2 , 501.2729)。
NMR (CDCl 3 , 300 MHz), δ: 0.79 (s, 3H, 18-CH 3 ), 2-(3-乙酰氧基-17-孕甾)-5,6-二甲基苯并咪唑
1.03 (s, 3H, 19-CH 3 ), 2.02 (s, 3H, 3-OCOCH 3 ), 3.74 (5g)，白色固体, 产率 68.1%，m.p. 120~123 ℃;
(s, 3H, 5-OCH 3 ), 4.57~4.63 (m, 1H, 3-αH), 5.38 (d, J 1 HNMR (CDCl 3 ，300 MHz), δ: 0.81 (s, 3H, 18-CH 3 ),
=2.4, 1H, 6-H), 6.32 (s, 1H, 4-H), 6.94 (d, 1H, 6-H), 1.05 (s, 3H, 19-CH 3 ), 2.04 (s, 3H, 3-CH 3 CO), 2.11 (s,
6.96 (d, J = 4.5, 1H, 7-H); 13 CNMR (75MHz, 3H, 4-CH 3 ), 2.26 (s, 3H, 5-CH 3 ), 4.57~4.68 (m, 1H,
DMSO-d 6 ), δ: 13.50 (18-C), 19.45 (19-C), 21.13 3-αH), 5.40 (d, J = 1.5, 1H, 6-H), 6.62 (d, J = 8.1, 1H,
(11-C), 21.57 (3-CH 3 CO), 23.96 (15-C), 24.71 6-H), 6.93 (d, J = 8.1, 1H, 7-H), 7.09 (s, 1H, N-H);
(16-C), 27.85 (2-C), 31.93 (8-C), 32.05 (7-C), 36.79 13 CNMR (75 MHz, DMSO-d 6 ), δ: 13.34 (4-C), 13.38