78.99, 55.23, 52.97, 48.66, 47.56, 42.24, 39.74, 39.14, 38.86, 38.76, 38.67, 36.98, 36.58, 33.18, 30.94, 30.66, 28.16, 28.14,
+
27.22, 24.30, 23.47, 23.37, 21.17, 18.32. HR-MS-ESI m/z 68.4854, C H O Na [M + Na] , calcd 685.4256.
45 58
4
–1
4ꢂ-Methyl-4-chalcone Ursolate (6b). Yield 72%, yellow powder, mp 132–134ꢁC. IR (KBr, ꢃ, cm ): 3441, 2925,
2869, 1748, 1700, 1663, 1601, 1506, 1453, 1210, 1162, 1090, 1024, 976, 690. H NMR (400 MHz, CDCl , ꢄ, ppm, J/Hz):
1
3
0.79 (3H, s, CH ), 0.89 (3H, d, J = 6.4, CH ), 0.90 (3H, d, J = 6.0, CH ), 0.94 (3H, s, CH ), 0.99 (3H, d, J = 6.0, CH ), 1.14
3
3
3
3
3
(3H, s, CH ), 1.35 (2H, t, J = 6.4, 4.2, CH ), 1.50 (2H, t, J = 8.4, 7.6, CH ), 1.91 (2H, t, J = 4.4, CH ), 2.17 (3H, s, CH ), 2.35 (1H,
3
2
2
2
3
13
d, J = 11.2, H-18), 5.34 (1H, s, OH), 6.98–7.97 (8H, m, PhH), 7.45 (1H, d, J = 12.0, ꢆ-H), 7.79 (1H, d, J = 12.5, ꢀ-H). C NMR
(100 MHz, CDCl , ꢄ): 184.62, 170.45, 147.56, 138.42, 138.21, 132.51, 130.36, 127.13, 125.43, 124.22, 124.09, 123.86,
3
123.40, 120.89, 116.70, 73.73, 50.00, 47.73, 47.67, 43.41, 43.29, 42.32, 37.00, 36.95, 34.51, 34.47, 33.90, 33.62, 33.51,
31.74, 31.34, 27.94, 25.42, 24.03, 22.93, 21.98, 19.06, 18.13, 18.13, 16.44, 15.92, 13.08, 12.38, 11.75, 10.28. HR-MS-ESI m/z
+
699.4403, C H O Na [M + Na] , calcd 699.4384.
46 60
4
–1
4ꢂ-Methoxy-4-chalcone Ursolate (6c). Yield 74%, yellow powder, mp 120–122ꢁC. IR (KBr, ꢃ, cm ): 3446, 2925,
1
2869, 1747, 1658, 1601, 1505, 1457, 1212, 1164, 1025, 974, 833. H NMR (400 MHz, CDCl , ꢄ, ppm, J/Hz): 0.71 (3H, s,
3
CH ), 0.79 (3H, s, CH ), 0.88 (3H, s, CH ), 0.91 (3H, d, J = 6.4, CH ), 0.94 (3H, s, CH ), 0.99 (3H, d, J = 6.0, CH ), 1.00 (3H,
3
3
3
3
3
3
s, CH ), 1.33 (2H, t, J = 6.4, 4.2, CH ), 1.52 (2H, t, J = 8.4, 7.6, CH ), 1.91 (2H, t, J = 4.4, CH ), 2.34 (1H, d, J = 11.2, H-18),
3
2
2
2
13
3.90 (3H, s, OCH ), 5.34 (1H, s, OH), 6.98–8.02 (8H, m, PhH), 7.51 (1H, d, J = 12.0, ꢆ-H), 7.79 (1H, d, J = 12.0, ꢀ-H). C NMR
3
(100 MHz, CDCl , ꢄ): 188.57, 175.71, 163.75, 163.46, 152.73, 143.03, 137.76, 137.34, 132.46, 131.37, 131.05, 130.82,
3
130.58, 130.05, 129.42, 126.13, 122.17, 121.74, 121.41, 113.86, 78.96, 69.55, 55.50, 55.25, 53.83, 52.96, 48.65, 48.53, 47.57,
42.24, 39.75, 39.13, 38.76, 36.98, 36.58, 33.18, 31.74, 30.67, 29.27, 28.17, 27.22, 24.29, 23.47, 21.17, 18.33, 17.63, 17.00,
+
15.68, 15.52. HR-MS-ESI m/z 715.4491, C H O Na [M + Na] , calcd 715.4416.
46 60
5
–1
4ꢂ-Chloro-4-chalcone Ursolate (6d). Yield 67%, yellow powder, mp 138–140ꢁC. IR (KBr, ꢃ, cm ): 3446, 2925,
1
2869, 1747, 1664, 1596, 1505, 1454, 1210, 1163, 1090, 1003, 975, 827. H NMR (400 MHz, CDCl , ꢄ, ppm, J/Hz): 0.71 (3H,
3
s, CH ), 0.79 (3H, s, CH ), 0.88 (3H, s, CH ), 0.89 (3H, d, J = 6.4, CH ), 0.94 (3H, s, CH ), 0.99 (3H, d, J = 6.0, CH ), 1.14
3
3
3
3
3
3
(3H, s, CH ), 1.33 (2H, t, J = 6.4, 4.2, CH ), 1.52 (2H, t, J = 8.4, 7.6, CH ), 1.91 (2H, t, J = 4.4, CH ), 2.35 (1H, d, J = 11.2, H-18),
3
2
2
2
13
5.32 (1H, s, OH), 6.98–7.97 (8H, m, PhH), 7.43 (1H, d, J = 12.0, ꢆ-H), 7.79 (1H, d, J = 12.0, ꢀ-H). C NMR (100 MHz,
CDCl , ꢄ): 189.02, 175.69, 153.06, 144.40, 139.28, 139.24, 137.75, 136.47, 132.06, 130.35, 129.91, 129.61, 128.96, 126.14,
3
122.29, 121.50, 121.32, 78.98, 55.23, 52.97, 52.91, 48.67, 48.55, 47.55, 42.24, 42.19, 39.74, 39.71, 39.13, 38.86, 38.84,
38.76, 38.67, 36.98, 36.58, 33.17, 30.65, 28.16, 27.22, 24.30, 23.47, 23.37, 21.16, 18.31, 17.62, 17.56, 16.99, 15.66, 15.52.
+
HR-MS-ESI m/z 719.3891, C H O ClNa [M + Na] , calcd 719.3916.
45 57
4
–1
4ꢂ-Fluoro-4-chalcone Ursolate (6e). Yield 66%, yellow powder, mp 124–126ꢁC. IR (KBr, ꢃ, cm ) : 3442, 2926,
1
2870, 1749, 1701, 1664, 1601, 1505, 1455, 1209, 1159, 1090, 1027, 976, 836. H NMR (400 MHz, CDCl , ꢄ, ppm, J/Hz):
3
0.72 (3H, s, CH ), 0.79 (3H, s, CH ), 0.89 (3H, s, CH ), 0.94 (3H, d, J = 6.4, CH ), 0.99 (3H, s, CH ), 1.00 (3H, d, J = 6.0,
3
3
3
3
3
CH ), 1.14 (3H, s, CH ), 1.33 (2H, t, J = 6.4, 4.2, CH ), 1.56 (2H, t, J = 8.4, 7.6, CH ), 1.89 (2H, t, J = 4.4, CH ), 2.38 (1H, d,
3
3
2
2
2
13
J = 11.2, H-18), 5.34 (1H, s, OH), 6.79–7.80 (8H, m, PhH), 7.43 (1H, d, J = 12.0, ꢆ-H), 7.75 (1H, d, J = 12.0, ꢀ-H). C NMR
(100 MHz, CDCl , ꢄ): 188.67, 175.69, 166.45, 164.77, 152.99, 144.10, 137.75, 134.49, 132.12, 131.12, 131.06, 130.69,
3
129.56, 126.13, 122.26, 121.47, 121.40, 115.83, 115.68, 78.93, 55.23, 52.97, 48.66, 47.55, 42.24, 42.19, 39.74, 39.13, 38.86,
38.76, 38.67, 36.98, 36.58, 33.17, 30.93, 30.65, 29.27, 28.16, 28.13, 27.22, 24.29, 23.47, 23.37, 21.16, 18.31, 17.62, 17.04,
+
16.99, 15.66, 15.52. HR-MS-ESI m/z 703.4411, C H O FNa [M + Na] , calcd 703.4316.
45 57
4
1-Acetyl-3-phenyl-4,5-dihydro-2-pyrazoline-5-phenyl Ursolate (7a). Yield 48%, white powder, mp 166–168ꢁC.
–1
1
IR (KBr, ꢃ, cm ): 3455, 2926, 2869, 1746, 1668, 1507, 1448, 1203, 1165, 1028, 853. H NMR (400 MHz, DMSO-d , ꢄ, ppm,
6
J/Hz): 0.74 (3H, s, CH ), 0.77 (3H, s, CH ), 0.83 (3H, d, J = 2.4, CH ), 0.86 (3H, d, J = 1.2, CH ), 0.91 (3H, s, CH ), 0.99 (3H,
3
3
3
3
3
s, CH ), 1.12 (3H, s, CH ), 1.35 (2H, t, J = 6.4, J = 4.2, CH ), 1.50 (2H, t, J = 8.4, 7.6, CH ), 1.91 (2H, t, J = 4.4, CH ), 2.31
3
3
2
2
2
(1H, d, J = 11.2, H-18), 2.41 (3H, s, COCH ), 3.20 (2H, t, J = 4.0, CH C=N), 3.80 (1H, t, J = 8.0, PhCHN), 5.28 (1H, s, OH),
3
2
13
6.95–7.74 (9H, m, PhH). C NMR (100 MHz, DMSO-d , ꢄ): 175.02, 167.36, 154.07, 149.64, 139.69, 137.55, 131.01, 130.27,
6
128.72, 126.69, 126.59, 125.30, 121.62, 76.76, 58.86, 54.71, 52.52, 47.42, 46.94, 41.97, 41.74, 38.33, 38.28, 38.22, 36.45,
36.07, 32.72, 30.65, 29.96, 29.56, 28.45, 28.20, 27.51, 26.94, 23.75, 23.10, 22.86, 21.67, 20.88, 17.92, 17.26, 16.83, 16.03,
+
15.21. HR-MS-ESI m/z 719.4780, C H O N [M] , calcd 719.4788.
47 62
4 2
1-Acetyl-3-(4-methylphenyl)-4,5-dihydro-2-pyrazoline-5-phenyl Ursolate (7b). Yield 48%, white powder,
–1
1
mp 172–174ꢁC. IR (KBr, ꢃ, cm ): 3443, 2925, 2868, 1746, 1666, 1508, 1450, 1204, 1164, 1096, 813. H NMR (400 MHz,
DMSO-d , ꢄ, ppm, J/Hz): 0.75 (3H, s, CH ), 0.77 (3H, s, CH ), 0.84 (3H, d, J = 2.4, CH ), 0.86 (3H, s, CH ), 0.92 (3H, d, J = 1.2,
6
3
3
3
3
CH ), 0.99 (3H, s, CH ), 1.12 (3H, s, CH ), 1.36 (2H, t, J = 6.4, CH ), 1.44 (3H, d, J = 3.2, CH ), 1.51 (2H, t, J = 8.4, J = 7.6, CH ),
3
3
3
2
3
2
63