Page 114 - 201812

·2082· 精细化工 FINE CHEMICALS 第 35 卷

(18-CH 3 ), 19.31 (19-C), 20.55 (5-CH 3 ), 21.01 (11-C), 0.1 mol/L K 2 CO 3 水溶液 1 mL 和甲醇 5 mL，常温搅
21.43 (3-CH 3 CO), 23.81 (15-C), 24.59 (16-C), 27.73 拌反应 2.5 h, TLC 跟踪，至无原料点后终止反应〔流
(2-C), 31.81 (8-C), 31.92 (7-C), 36.66 (1-C), 37.04 动相 V（乙酸乙酯）∶V（石油醚）= 1∶1〕。将反
(10-C), 38.07 (4-C), 38.59 (12-C), 44.14 (17-C),
50.02 (9-C), 56.43 (13-C), 57.35 (14-C), 73.89 应物减压蒸去溶剂，然后加入 10 mL 蒸馏水，再用
(3-C), 120.48 (7-C), 122.21 (6-C), 122.34 (4-C), 二氯甲烷分 3 次萃取，合并有机相，饱和食盐水洗
122.70 (6-C), 122.80 (8-C), 135.09 (5-C), 139.49 涤，无水 Na 2 SO 4 干燥，滤液减压除去溶剂得白色固
(9-C), 139.69 (5-C), 170.64 (2-C), 171.75 (C==O); IR 体, 进一步柱层析分离得到目标产物 6a~6i〔流动相
–1
(KBr), ν/cm : 3361, 2935, 2900, 1733, 1509, 1369, V（乙酸乙酯）∶V（石油醚）= 1∶1〕。
+
1242, 1035, 786, 729; HREIMS, m/Z: 461.3164 [M+H]
(calcd for C 30H 40N 2O 2, 461.3168)。 2-(3-羟基-17-孕甾)苯并咪唑(6a), 白色固体,
1
2-(3-乙酰氧基-17'-孕甾)-5-甲基-6-溴苯并咪唑 产率 89.6% ， m.p.124~126 ℃ ; HNMR (CDCl 3 ,
300 MHz), δ: 0.83 (s, 3H, 18-CH 3 ), 1.04 (s, 3H,
(5h)，淡黄色固体, 产率 11.6%, m.p. 105~107 ℃;
1 19-CH 3), 3.50~3.60 (m, 1H, 3-αH), 3.89 (br s, 1H,
HNMR (CDCl 3 , 300 MHz), δ: 0.80 (s, 3H, 18-CH 3 ), 3-OH), 5.38 (d, J = 4.8, 1H, 6-H), 6.82 (d, J = 7.5, 2H,
1.05 (s, 3H, 19-CH 3 ), 2.04 (s, 3H, 3-OCOCH 3 ), 2.19 5-H 和 6-H), 7.03 (s, 1H, N-H), 7.06 (d, J = 7.5, 1H,
(s, 3H, 5-CH 3 ), 4.57~4.66 (m, 1H, 3-αH), 5.40 (d, J = 13
4.5, 1H, 6-H), 6.79 (s, 1H, N-H), 7.10 (s, 1H, 4-H), 3-H), 7.19 (d, J = 7.5, 1H, 7-H); CNMR (75 MHz,
DMSO-d 6 ), δ: 13.31 (18-C), 19.38 (19-C), 21.07
13
7.25 (s, 1H, 7-H); CNMR (75 MHz, DMSO-d 6 ), δ: (11-C), 23.82 (15-C), 24.57 (16-C), 31.62 (8-C),
13.39 (18-C), 17.64 (5-CH 3 ), 19.30 (19-C), 21.00 31.81 (2-C), 31.98 (7-C), 36.58 (10-C), 37.30 (1-C),
(11-C), 21.41 (3-CH 3 CO), 23.81 (15-C), 24.58 38.70 (12-C), 42.26 (4-C), 44.19 (17-C), 50.11 (9-C),
(16-C), 27.72 (2-C), 29.69 (8-C), 31.92 (7-C), 36.66 56.54 (13-C), 57.59 (14-C), 71.71 (3-C), 118.34 (4-C
(1-C), 37.05 (10-C), 38.06 (4-C), 38.58 (12-C), 和 7-C), 119.55 (5-C 和 6-C), 121.37 (6-C), 125.06
44.25 (17-C), 49.99 (9-C), 56.43 (13-C), 58.43
(14-C), 73.902 (3-C), 109.90 (7-C), 122.30 (6-C), (9-C), 126.96 (8-C), 140.81 (5-C), 171.49 (2-C); IR
–1
125.40 (6-C), 125.89 (4-C), 126.52 (8-C), 130.66 (KBr), ν/cm : 3357, 2926, 2851, 1653, 1589, 1380,
1457, 1045, 956, 745; HREIMS, m/Z : 391.2791
(5-C), 138.47 (9-C), 139.70 (5-C), 170.74 (2-C), +
–1
171.85 (3-OCOCH 3 ); IR (KBr), ν/cm : 2937, [M+H] (calcd for C 26 H 35 N 2 O, 391.2749)。
2867,1786, 1726, 1589, 1372, 1115, 1030, 901, 794; 2-(3-羟基-17-孕甾)-5-氯苯并咪唑 (6b), 白色
1
HREIMS, m/Z: 525.2101 [M+H] + (calcd for 固体, 产率：95.0%，m.p，93~95 ℃; HNMR (CDCl 3 ,
C 29 H 37 BrN 2 O 2 , 525.2117)。 300 MHz), δ: 0.80 (s, 3H, 18-CH 3 ), 1.04 (s, 3H,
2-(3-乙酰氧基-17-孕甾)-6,7-二甲基苯并咪唑 19-CH 3 ), 3.49~3.59 (m, 1H, 3-αH), 5.38 (d, J = 4.5,
1H, 6-H), 6.97 (d, J = 8.1, 1H, 6-H), 7.24 (d, J = 8.1,
(5i)，淡黄色固体,产率 11.5%, m.p. 108~110 ℃;
1 HNMR (CDCl 3 ，300 MHz), δ: 0.81 (s, 3H, 18-CH 3 ), 1H, 7-H), 7.75 (s, 1H, N-H), 7.90 (s, 1H, 4-H);
13
CNMR (75 MHz, DMSO-d 6 ), δ: 13.31 (18-C), 19.41
1.05 (s, 3H, 19-CH 3), 2.05 (s, 3H, 3-CH 3CO), 2.15 (s, (19-C), 20.98 (11-C), 23.79 (15-C), 24.60 (16-C),
3H, 5-CH 3 ), 2.17 (s, 3H, 6-CH 3 ), 4.57~4.68 (m, 1H, 31.60 (8-C), 31.81 (2-C), 31.95 (7-C), 36.56 (10-C),
3-αH), 5.40 (d, J = 4.8, 1H, 6-H), 6.61 (s, 1H, 3-H), 37.30 (1-C), 38.51 (12-C), 42.23 (4-C), 44.28
6.94 (s, 1H, 6-H), 7.07 (s, 1H, N-H); 13 CNMR (17-C), 50.10 (9-C), 56.44 (13-C), 57.64 (14-C),
(75 MHz, DMSO-d 6 ), δ: 13.30 (18-C), 18.74 71.70 (3-C), 121.35 (6-C), 125.40 (4-C), 125.72
(19-CH 3 ), 19.31 (6-CH 3 ), 19.31 (5-CH 3 ), 21.02 (7-C), 127.92 (6-C), 130.75 (5-C), 136.20 (9-C),
(11-C), 21.41 (3-CH 3 CO), 23.83 (15-C), 24.58 140.47 (8-C), 140.83 (5-C), 172.20 (2-C); IR (KBr),
–1
(16-C), 27.74 (2-C), 31.81 (8-C), 31.93 (7-C), 36.66 ν/cm : 3359, 2922, 2852, 1651, 1516, 1377, 1045,
+
(1-C), 37.05 (10-C), 38.08 (4-C), 38.57 (12-C), 789, 731; HREIMS, m/Z: 425.2359 [M+H] (calcd for
44.12 (17-C), 50.03 (9-C), 56.43 (13-C), 57.41 C 26 H 33 ClN 2 O, 425.2360)。
(14-C), 73.88 (3-C), 119.72 (7-C), 122.33 (4-C), 2-(3-羟基-17-孕甾)-5-氟苯并咪唑 (6c)，白色
122.40 (6-C), 126.03 (8-C), 127.56 (9-C), 135.22 固体，产率 95.1%，m.p. 225~227 ℃; HNMR (CDCl 3 ，
1
(6-C), 138.30 (5-C), 139.71 (5'-C), 170.60 (2-C), 600 MHz), δ: 0.80 (s, 3H, 18-CH 3 ), 1.02 (s, 3H,
–1
171.39 (3'-OCOCH 3 ); IR (KBr), ν/cm : 3438, 2930,
2855, 1663, 1731, 1521, 1379, 1025, 871, 796; 19-CH 3 ), 3.10~3.55 (m, 1H, 3-αH), 5.36 (s, 1H, 6-H),
HREIMS, m/Z: 461.3170 [M+H] + (calcd for 6.47 (s, 1H, OH), 6.44~6.49 (m, 1H, 6-H), 6.89 (s, 1H,
13
4-H), 7.023 (t, J = 7.2, 1H, 7-H); CNMR (150 MHz,
C 30 H 40 N 2 O 2 , 461.3168)。
DMSO-d 6 ), δ: 13.00 (18-C), 19.02 (19-C), 20.68
1.2.3 2-(3- 羟基 -17- 孕甾 ) 苯并咪 唑类化合物 (11-C), 23.44 (15-C), 24.18 (16-C), 31.21 (2-C),
(6a~6i)的合成 31.41 (7-C), 31.58 (8-C), 36.18 (12-C), 36.90 (1-C),
称取 0.16mmol 化合物 5 放入圆底烧瓶中，加入 38.34 (10-C), 41.85 (4-C), 43.81 (13-C), 49.68