Page 59 - 《中国药科大学学报》2025年第4期

第 56 卷第 4 期 陈 果，等：积雪草酸衍生物的合成及抗肿瘤活性测定 455

1.2.6 N-[2α, 3β, 23-三羟基-乌索烷型-12-烯-28- 3 -丙二胺 (0.11 mL, 1.2 mmol)、EDCI (168 mg, 0.8
酰 ]-1, 3-丙二胺 (AA-4) 的合成 向溶有 AA (200 mmol) 和 DMAP (3.45 mg, 0.04 mmol)。 然 后 在
mg, 0.4 mmol) 的 DMF (10 mL) 溶液中，依次加入 1, 80 ℃ 下反应 12 h，TLC 检测反应。反应完成后，向
反应液中加入 10 mL 水进行稀释，用少量乙酸乙酯

Table 1 Yield, melting point and MS data of compounds AA-1-II 3
Compd. Yield Melting/°C ESI-MS m/z[M+H] + 萃取 3 次，旋蒸除去溶剂，粗产物经硅胶柱色谱纯
AA-1 89.3% 151.0−152.7 615.82 化（石油醚-乙酸乙酯，15∶1)，得到白色固体 AA-4。

AA-2 85.7% 151.0−152.7 671.46
1.2.7 N-[2α, 3β, 23-三羟基-乌索烷型-12-烯-28-
AA-3 72.1% 176.2−176.9 658.42
酰 ]-(3-氨基丙基)-(4-氟苯甲酰胺) (AA-5) 的合成
I 1 63.1% 177.4−178.5 843.34
65.1% 177.2−178.5 774.44 向溶有 AA-4 (127 mg, 0.23 mmol) 的
I 2 CH Cl (5 mL)
2
2
中，在冰浴条件下依次缓慢滴加到 4-氟苯甲酰氯
I 3 62.4% 175.2−176.4 794.24
63.1% 165.8−166.7 754.51
I 4
(0.081 mL, 0.69 mmol)。 将 TEA (0.05 mL, 0.46
64.1% 176.2−177.4 754.51
I 5
I 6 62.4% 174.2−175.4 757.00 mmol) 和少量 DMAP (1.7 mg, 0.02 mmol) 在室温下
61.8% 172.2−173.4 797.43
I 7 搅拌 5 h，用 TLC 检测反应。反应结束后，向反应液
I 8 63.4% 174.2−176.4 779.51
中加入 10 mL 水进行稀释，用少量乙酸乙酯萃取
62.7% 175.5−176.4 793.45
I 9
AA-4 62.1% 174.2−175.4 545.42 3 次，旋蒸除去溶剂，粗产物经硅胶柱色谱纯化（石
AA-5 69.1% 175.2−176.4 667.44 油醚-乙酸乙酯，15∶1) 提纯有机层的干原油。得到
AA-6 61.7% 181.2−183.4 717.44
白色固体 AA-5。
AA-7 61.1% 171.2−174.4 685.43
1.2.8 N-[2α, 3β, 23-三羟基-乌索烷型-12-烯-28-酰 ]-
II 1 54.8% 176.2−177.4 708.49
53.1% 176.4−178.4 726.45 (3-氨基丙基)-(4-三氟甲基苯甲酰胺) (AA-6) 的合成 按
II 2
58.1% 175.2−176.7 758.48
照化合物 AA-5 的合成方法，以化合物 AA-4 (127
II 3

1 13
Table 2 H NMR and C NMR data of compounds I 1 −II 3
Compd. 1 H NMR (400 MHz) 13 C NMR (100 MHz)
I 1 (Chloroform-d) δ 8.02 (d, J = 8.0 7.84 (t, J = 6.2 Hz, 1 H), 7.70 (d, J = (Chloroform-d) δ 179.75, 174.04, 173.97, 173.66, 166.07,
8.1 Hz, 2 H), 6.28 (t, J = 6.4 Hz, 1 H), 5.36 (d, J = 3.8 Hz, 1 H), 5.18 139.90, 137.86, 133.11, 132.78, 130.37 (2 C), 127.66 (2 C),
(td, J 1 = 10.7, J 2 = 4.3 Hz, 1 H), 5.11 (d, J = 10.3 Hz, 1 H), 3.88 (d, 125.57, 125.53, 74.37, 69.69, 64.91, 53.76, 48.01, 47.62,
J = 11.8 Hz, 1 H), 3.73 (dd, J 1 = 13.7, J 2 = 6.7 Hz, 1 H), 3.55 (t, J = 47.44, 43.85, 42.54, 42.08, 39.80, 39.59, 39.03, 37.76,
12.0 Hz, 2 H), 3.12 (dd, J 1 = 28.0, J 2 = 4.7 Hz, 2 H), 2.37 (s, 3 H), 36.14, 35.89, 32.18, 30.81, 27.82, 27.70, 24.80, 23.48,
2.27 (s, 3 H), 2.00 (s, 3 H), 1.91 (d, J = 11.3 Hz, 2 H), 1.08 (d, J = 23.09, 21.20, 17.83, 17.20, 17.00, 16.87, 13.94, 9.31, 9.25,
8.1 Hz, 6 H), 0.95 (s, 3 H), 0.88 (d, J = 9.9 Hz, 6 H), 0.78 (s, 3 H). 9.11.
(Chloroform-d) δ 8.11 – 7.84 (m, 2 H), 7.46 (dd, J 1 = 15.0, J 2 = 7.2 (Chloroform-d) δ 177.84, 172.12, 171.84, 171.45, 164.25,
I 2
Hz, 3 H), 7.33 (t, J = 6.3 Hz, 1 H), 6.35 (t, J = 6.2 Hz, 1 H), 5.38 (d, 137.72, 135.64, 131.02, 130.56, 128.26(2C), 125.43(2C),
J = 3.9 Hz, 1 H), 5.16 (td, J 1 = 10.9, J 2 = 4.5 Hz, 1 H), 5.08 (d, J = 123.41, 74.35, 69.49, 64.71, 53.56, 47.81, 47.60, 47.24,
10.3 Hz, 1 H), 3.85 (d, J = 11.8 Hz, 1 H), 3.67 (d, J = 6.8 Hz, 1 H), 43.65, 42.34, 42.18, 39.70, 39.69, 39.52, 37.74, 36.04,
3.56 (dd, J 1 = 20.1, J 2 = 10.1 Hz, 2 H), 3.23 (d, J = 4.9 Hz, 1 H), 35.67, 32.06, 31.61, 27.62, 27.50, 25.60, 23.38, 21.09,
3.09 (d, J = 5.4 Hz, 1 H), 2.08 (s, 3 H), 2.02 (s, 3 H), 1.99 (s, 3 H), 21.10, 17.63, 17.01, 16.90, 16.67, 13.84, 9.21, 9.15, 9.01
0.95 (s, 6 H), 0.87 (d, J = 8.1 Hz, 9H), 0.78 (s, 3 H).
(Chloroform-d) δ 8.11 – 7.70 (m, 2 H), 7.50 (t, J = 5.3 Hz, 1 H), 7.18 (Chloroform-d) δ 178.75, 173.24, 172.87, 172.56, 165.37,
I 3
– 7.01 (m, 2 H), 6.30 (t, J = 6.4 Hz, 1 H), 5.37 (t, J = 3.9 Hz, 1 H), 164.74, 138.81, 136.76, 132.34, 127.65(2C), 125.43(2C),
5.16 (td, J 1 = 10.8, J 2 = 4.4 Hz, 1 H), 5.08 (d, J = 10.3 Hz, 1 H), 74.34, 69.59, 64.81, 53.66, 47.91, 47.61, 47.44, 43.85,
3.85 (dd, J 1 = 11.8, J 2 = 2.6 Hz, 1 H), 3.68 (d, J = 6.7 Hz, 1 H), 3.58 42.54, 42.08, 39.80, 39.59, 39.02, 37.76, 36.14, 35.89,
(d, J = 11.8 Hz, 2 H), 3.13 (dd, J 1 = 33.9, J 2 = 5.0 Hz, 2 H), 2.08 (s, 32.18, 30.81, 27.82, 27.70, 24.80, 23.48, 23.09, 21.20,
3 H), 2.03 (s, 3 H), 1.98 (d, J = 2.1 Hz, 3 H), 1.92 (d, J = 2.4 Hz, 2 17.83, 17.21, 17.00, 16.87, 13.94, 9.32, 9.25, 9.10.
H), 1.10 (d, J = 4.9 Hz, 6 H), 0.96 (s, 3 H), 0.88 (d, J = 8.1 Hz, 6 H),
0.78 (s, 3 H).
I 4 (Chloroform-d) δ 6.27 (t, J = 6.1 Hz, 1 H), 6.26 – 6.15 (t, J = 6.4 Hz, (Chloroform-d) δ 178.75, 174.14, 174.05, 173.74, 158.97,
1 H), 5.29 (s, 1 H), 5.09 (td, J 1 = 10.8, J 2 = 4.5 Hz, 1 H), 5.01 (d, J = 139.72, 125.30, 77.48, 76.84, 69.81, 65.02, 53.63, 47.89,
10.3 Hz, 1 H), 3.38 – 3.33 (m, 1 H), 3.11 (dd, J 1 = 42.4, J 2 = 6.4 Hz, 47.76, 47.56, 43.96, 42.54, 42.18, 39.85, 39.69, 39.09,
1 H), 2.96 (d, J = 6.1 Hz, 1 H), 2.01 (s, 3 H), 1.96 (s, 3 H), 1.92 (s, 3 37.87, 37.58, 37.13, 36.31, 35.70, 32.37, 30.99, 30.49,
H), 1.59 (s, 2 H), 1.03 (s, 6 H), 0.89 (s, 6 H), 0.87 (s, 3 H), 0.82 (s, 3 27.91, 27.80, 27.00, 24.78, 23.54, 23.23, 21.32, 17.95,
H), 0.80 (s, 3 H), 0.70 (s, 3 H). 17.27, 17.09, 16.99, 14.04, 9.40, 9.33, 9.19.