Luận án Nghiên cứu thành phần hóa học và hoạt tính sinh học của lá Schefflera sessiliflora De P. V. thuộc họ ngũ gia bì (araliaceae) ở Việt Nam

(C-28), 33,2 (C-29), 23,7 (C- 30), 104,8 (C-1), 74,7 (C-2), 78,2 (C-3), 73,5 (C-4), 76,6 (C-5). Phổ 1H NMR (500 MHz, pyridine-d5,  ppm): 4,25-4,34 (1H, m, H-3), 5,43 (1H, br s, H-12), 3,25 (1H, br d, J = 13,5 Hz, H-18), 4,25-4,34 (H, m, H-23a), 3,63 (1H, d, J = 11,0 Hz, H23b), 0,90 (3H, s, H-24), 0,87 (3H, s, H-25), 0,98 (3H, s, H-26), 1,23 (3H, s, H-27), 0,90 (3H, s, H-29), 0,97 (3H, s, H-30), 5,10 (1H, d, J = 7,0 Hz, H- 44 1), 4,05 (1H, t, J = 8,0 Hz, H-2), 4,15 (1H, t, J = 8,5 Hz, H-3), 4,25-4,34 (1H, m, H- 4), 4,25-4,34 (1H, m, H-5). 3.3.4. Acid 3-O-[α-L-rhamnopyranosyl-(13)]--D-glucuronopyranosyloleanolic (SS17) Dạng bột, màu trắng. Phổ HR-ESI-MS: negative m/z: 777,4443. Phổ 13C NMR (125 MHz, pyridine-d5,  ppm): 38,4 (C-1), 25,9 (C-2), 89,2 (C- 3), 39,0 (C-4), 55,4 (C-5), 18,0 (C-6), 32,7 (C-7), 39,2 (C-8), 47,5 (C-9), 36,4 (C-10), 23,4 (C-11), 122,1 (C-12), 144,4 (C-13), 41,7 (C-14), 27,8 (C-15), 23,2 (C-16), 46,4 (C-17), 41,5 (C-18), 46,4 (C-19), 30,5 (C-20), 33,7 (C-21), 32,7 (C-22), 27,8 (C-23), 16,6 (C-24), 15,0 (C-25), 17,0 (C-26), 25,8 (C-27), 180,5 (C-28), 32,9 (C-29), 23,4 (C- 30), 106,0 (C-1), 75,3 (C-2), 81,9 (C-3), 71,8 (C-4), 76,0 (C-5), 101,8 (C-1), 71,6 (C-2), 71,9 (C-3), 73,5 (C-4), 69,2 (C-5), 18,0 (C-6). Phổ 1H NMR (500 MHz, pyridine-d5,  ppm): 3,25 (1H, dd, J = 3,5 và 12,0 Hz, H-3), 5,37 (1H, br s, H-12), 3,15 (1H, br d, J = 9,5 Hz, H-18), 1,16 (3H, s, H-23), 0,87 (3H, s, H-24), 0,67 (3H, s, H-25), 0,84 (3H, s, H-26), 1,19 (3H, s, H-27), 0,87 (3H, s, H-29), 0,93 (3H, s, H-30), 4,72 (1H, d, J = 8,0 Hz, H-1), 3,92 (1H, t, J = 8,5 Hz, H- 2), 4,18-4,28 (1H, t, J = 8,5 Hz, H-3), 4,06-4,10 (1H, m, H-4), 4,21 (1H, d, J = 9,5 Hz, H-5), 6,12 (1H, br s, H-1), 4,62 (1H, dd, J = 1,5 và 3,0 Hz, H-2), 4,46 (1H, dd, J = 3,5 và 9,5 Hz, H-3), 4,21 (1H, t, J = 9,5 Hz, H-4), 4,89 (1H, dd, J = 9,5 và 6,0 Hz, H-5), 1,60 (1H, d, J = 6,0 Hz, H-6). 3.3.5. 3-O-[α-L-rhamnopyranosyl-(13)]--D-glucuronopyranosylhederagenin (SS18) Dạng bột, màu trắng. Phổ HR-ESI-MS: negative m/z: 793,4368. Phổ 13C NMR (125 MHz, pyridine-d5,  ppm): 38,5 (C-1), 26,0 (C-2), 81,0 (C- 3), 43,3 (C-4), 47,3 (C-5), 18,1 (C-6), 32,8 (C-7), 39,7 (C-8), 48,0 (C-9), 36,7 (C-10), 23,6 (C-11), 122,4 (C-12), 144,9 (C-13), 42,0 (C-14), 28,2 (C-15), 23,7 (C-16), 46,6 (C-17), 41,9 (C-18), 46,4 (C-19), 30,9 (C-20), 34,1 (C-21), 33,2 (C-22), 64,0 (C-23), 13,5 (C-24), 15,9 (C-25), 17,4 (C-26), 26,1 (C-27), 180,0 (C-28), 33,2 (C-29), 23,7 (C- 30), 105,3 (C-1), 75,0 (C-2), 82,0 (C-3), 71,9 (C-4), 77,0 (C-5), 102,5 (C-1), 72,4 (C-2), 72,6 (C-3), 74,1 (C-4), 69,6 (C-5), 18,6 (C-6). 45 Phổ 1H NMR (500 MHz, pyridine-d5,  ppm): 4,23-4,26 (1H, m, H-3), 5,42 (1H, br s, H-12), 3,25 (1H, br d, J = 10,0 Hz, H-18), 4,23-4,26 (H, m, H-23a), 3,63 (1H, d, J = 11,0 Hz, H23b), 0,86 (3H, s, H-24), 0,84 (3H, s, H-25), 0,96 (3H, s, H-26), 1,23 (3H, s, H-27), 0,89 (3H, s, H-29), 0,96 (3H, s, H-30), 5,01 (1H, d, J = 6,5 Hz, H- 1), 3,98 (1H, m, H-2), 4,23-4,26 (1H, m, H-3), 4,23-4,26 (1H, m, H-4), 4,23-4,26 (1H, m, H-5), 6,24 (1H, br s, H-1), 4,72 (1H, br s, H-2), 4,56 (1H, br d, J = 7,0 Hz, H-3), 4,31 (1H, d, J = 9,5 Hz, H-4), 5,01 (1H, d, J = 6,5 Hz, H-5), 1,66 (1H, d, J = 5,5 Hz, H-6). 3.3.6. Chikusetsusaponin IVa (SS19) Dạng bột, màu trắng. Phổ HR-ESI-MS: positive m/z: 812,4713, 817,4385, 839,4134. Phổ 13C NMR (125 MHz, pyridine-d5,  ppm): 38,7 (C-1), 26,6 (C-2), 89,1 (C- 3), 39,5 (C-4), 55,7 (C-5), 18,5 (C-6), 33,1 (C-7), 39,9 (C-8), 48,0 (C-9), 36,9 (C-10), 23,7 (C-11), 122,9 (C-12), 144,1 (C-13), 42,1 (C-14), 28,2 (C-15), 23,4 (C-16), 47,0 (C-17), 41,7 (C-18), 46,2 (C-19), 30,8 (C-20), 34,0 (C-21), 32,5 (C-22), 28,2 (C-23), 16,9 (C-24), 15,5 (C-25), 17,5 (C-26), 26,1 (C-27), 176,4 (C-28), 33,1 (C-29), 23,6 (C- 30), 107,3 (C-1), 75,5 (C-2), 78,1 (C-3), 73,4 (C-4), 77,9 (C-5), 172,8 (C-6), 95,7 (C-1), 74,1 (C-2), 78,9 (C-3), 71,1 (C-4), 79,3 (C-5), 62,2 (C-6). Phổ 1H NMR (500 MHz, pyridine-d5,  ppm): 3,36 (1H, dd, J = 4,5 và 12,0 Hz, H-3), 5,40 (1H, br s, H-12), 3,18 (1H, dd, J = 3,5 và 13,5 Hz, H-18), 1,29 (3H, s, H- 23), 0,97 (3H, s, H-24), 0,81 (3H, s, H-25), 1,07 (3H, s, H-26), 1,26 (3H, s, H-27), 0,89 (3H, s, H-29), 0,87 (3H, s, H-30), 5,01 (1H, d, J = 8,0 Hz, H-1), 4,11-4,14 (1H, m, H-2), 4,33-4,34 (1H, m, H-3), 4,61 (1H, t, J = 9,0 Hz, H-4), 4,69 (1H, d, J = 9,5 Hz, H-5), 6,30 (1H, d, J = 8,5 Hz, H-1), 4,22-4,24 (1H, m, H-2), 4,28-4,30 (1H, m, H-3), 4,33-4,34 (1H, m, H-4), 4,01-4,11 (1H, m, H-5), 4,43-4,61 (1H, dd, J = 2,5 và 11,5 Hz, H-6a), 4,36-4,40 (1H, m, H-6b). 3.3.7. Chikusetsusaponin IVa methyl ester (SS14) Dạng bột, màu trắng. Phổ HR-ESI-MS: positive m/z: 831,4502. Phổ 13C NMR (125 MHz, pyridine-d5,  ppm): 38,7 (C-1), 26,5 (C-2), 89,1 (C- 3), 39,5 (C-4), 55,7 (C-5), 18,4 (C-6), 33,1 (C-7), 39,9 (C-8), 48,0 (C-9), 36,9 (C-10), 23,5 (C-11), 122,8 (C-12), 144,1 (C-13), 42,1 (C-14), 28,2 (C-15), 23,7 (C-16), 47,0 (C-17), 41,7 (C-18), 46,2 (C-19), 30,7 (C-20), 34,0 (C-21), 33,1 (C-22), 28,1 (C-23), 46 16,9 (C-24), 15,5 (C-25), 17,4 (C-26), 26,1 (C-27), 176,5 (C-28), 33,1 (C-29), 23,7 (C- 30), 107,2 (C-1), 75,3 (C-2), 77,9 (C-3), 73,1 (C-4), 77,2 (C-5), 170,8 (C-6), 52,0 (OMe), 95,7 (C-1), 74,1 (C-2), 78,8 (C-3), 71,1 (C-4), 79,3 (C-5), 62,2 (C-6). Phổ 1H NMR (500 MHz, pyridine-d5,  ppm): 3,33 (1H, dd, J = 4,0 và 11,5 Hz, H-3), 5,40 (1H, br s, H-12), 3,16 (1H, dd, J = 4,0 và 14,0 Hz, H-18), 1,28 (3H, s, H- 23), 0,95 (3H, s, H-24), 0,81 (3H, s, H-25), 1,06 (3H, s, H-26), 1,24 (3H, s, H-27), 0,89 (3H, s, H-29), 0,86 (3H, s, H-30), 4,96 (1H, d, J = 8,0 Hz, H-1), 4,07 (1H, t, J = 8,5 Hz, H-2), 4,22-4,28 (1H, m, H-3), 4,43-4,47 (1H, m, H-4), 4,57 (1H, d, J = 9,5 Hz, H-5), 3,71 (OMe), 6,28 (1H, d, J = 8,5 Hz, H-1), 4,18 (1H, t, J = 8,5 Hz, H-2), 4,22-4,28 (1H, m, H-3), 4,31 (1H, d, J = 9,0 Hz, H-4), 4,00-4,03 (1H, m, H-5), 4,43-4,47 (1H, m, H-6a), 4,34-4,39 (1H, m, H-6b). 3.3.8. Pseudoginsenoside RT1 methyl ester (SS15) Dạng bột, màu trắng. Phổ HR-ESI-MS: positive m/z: 963,4915. Phổ 13C NMR (125 MHz, CD3OD,  ppm): 39,8 (C-1), 27,1 (C-2), 91,3 (C-3), 40,3 (C-4), 57,1 (C-5), 19,3 (C-6), 34,0 (C-7), 40,7 (C-8), 49,0 (C-9), 37,9 (C-10), 23,7 (C-11), 123,8 (C-12), 144,8 (C-13), 42,9 (C-14), 28,9 (C-15), 24,5 (C-16), 48,0 (C-17), 42,6 (C-18), 47,2 (C-19), 31,5 (C-20), 34,9 (C-21), 33,1 (C-22), 28,2 (C-23), 16,5 (C-24), 16,0 (C-25), 17,7 (C-26), 26,3 (C-27), 178,1 (C-28), 33,5 (C-29), 24,0 (C- 30), 105,5 (C-1), 82,7 (C-2), 77,6 (C-3), 73,0 (C-4), 76,4 (C-5), 171,3 (C-6), 52,8 (OMe), 106,3 (C-1), 76,3 (C-2), 77,8 (C-3), 71,2 (C-4), 67,2 (C-5), 95,7 (C-1), 73,9 (C-2), 78,3 (C-3), 71,1 (C-4), 78,7 (C-5), 62,4 (C-6). Phổ 1H NMR (500 MHz, CD3OD,  ppm): 3,12-3,18 (1H, m, H-3), 5,27 (1H, br s, H-12), 2,88 (1H, dd, J = 4,5 và 14,0 Hz, H-18), 1,06 (3H, s, H-23), 0,85 (3H, s, H- 24), 0,97 (3H, s, H-25), 0,83 (3H, s, H-26), 1,17 (3H, s, H-27), 0,93 (3H, s, H-29), 0,95 (3H, s, H-30), 4,45 (1H, d, J = 7,5 Hz, H-1), 3,48-3,52 (1H, m, H-2), 3,56-3,61 (1H, m, H-3), 3,56-3,61 (1H, m, H-4), 3,81-3,88 (1H, m, H-5), 3,79 (OMe), 4,55 (1H, d, J = 7,5 Hz, H-1), 3,20-3,25 (1H, m, H-2), 3,33 (1H, m, H-3), 3,48-3,52 (1H, m, H-4), 3,81-3,88 (1H, m, H-5a), 3,12-3,18 (1H, m, H-5b), 5,40 (1H, d, J = 8,0 Hz, H-1), 3,33 (1H, m, H-2), 3,43-3,47 (1H, m, H-3), 3,35-3,38 (1H, m, H-4), 3,35- 3,38 (1H, m, H-5), 3,81-3,88 (1H, m, H-6a), 3,67-3,70 (1H, m, H-6b). 3.3.9. Scheffleraside C (SS16, chất mới) Dạng bột, màu trắng. ሾαሿୈଶହ-20.0 (c 0,10, MeOH). 47 Phổ HR-ESI-MS: positive m/z: 977,5073. Phổ UV (MeOH), λmax, nm: 192. Phổ IR (MeOH), νmax, cm-1: 3418, 2972, 2928, 1742, 1635, 1081, 1049. Phổ 13C NMR (125 MHz, pyridine-d5,  ppm): 38,6 (C-1), 26,4 (C-2), 89,1 (C- 3), 39,5 (C-4), 55,7 (C-5), 18,4 (C-6), 33,1 (C-7), 39,9 (C-8), 48,0 (C-9), 36,9 (C-10), 23,7 (C-11), 122,9 (C-12), 144,0 (C-13), 42,1 (C-14), 28,2 (C-15), 23,3 (C-16), 47,0 (C-17), 41,7 (C-18), 46,1 (C-19), 30,7 (C-20), 34,0 (C-21), 32,5 (C-22), 28,1 (C-23), 16,9 (C-24), 15,5 (C-25), 17,4 (C-26), 26,1 (C-27), 176,4 (C-28), 33,1 (C-29), 23,6 (C- 30), 107,2 (C-1), 75,4 (C-2), 77,9 (C-3), 73,1 (C-4), 77,2 (C-5), 170,8 (C-6), 52,0 (OMe), 95,4 (C-1), 74,2 (C-2), 77,0 (C-3), 77,9 (C-4), 77,9 (C-5), 61,0 (C-6), 102,7 (C-1), 72,5 (C-2), 72,6 (C-3), 73,9 (C-4), 70,4 (C-5), 18,5 (C-6). Phổ 1H NMR (500 MHz, pyridine-d5,  ppm): 3,33 (1H, dd, J = 4,5 và 11,5 Hz, H-3), 5,38 (1H, br s, H-12), 3,15 (1H, dd, J = 4,0 và 13,5 Hz, H-18), 1,28 (3H, s, H- 23), 0,95 (3H, s, H-24), 0,80 (3H, s, H-25), 1,05 (3H, s, H-26), 1,24 (3H, s, H-27), 0,89 (3H, s, H-29), 0,87 (3H, s, H-30), 4,96 (1H, d, J = 8,0 Hz, H-1), 4,04-4,09 (1H, m, H-2), 4,25 (1H, t, J = 8,5 Hz, H-3), 4,36 (1H, t, J = 9,5 Hz, H-4), 4,56-4,58 (1H, m, H-5), 3,74 (OMe), 6,20 (1H, d, J = 8,0 Hz, H-1), 4,12 (1H, t, J = 8,5 Hz, H-2), 4,15-4,21 (1H, m, H-3), 4,50-4,53 (1H, m, H-4), 3,77 (1H, m, H-5), 4,15-4,21 (1H, m, H-6a), 4,04-4,09 (1H, m, H-6b), 5,87 (1H, br s, H-1), 4,64 (1H, d, J = 1,5 Hz, H-2), 4,50-4,53 (1H, m, H-3), 4,31-4,34 (1H, m, H-4), 4,88-4,92 (1H, m, H-5), 1,66 (3H, d, J = 6,5 Hz, H-6). 3.3.10. Scheffleraside B (SS20, chất mới) Dạng bột, màu trắng. ሾαሿୈଶହ-13,5 (c 0,10, MeOH). Phổ HR-ESI-MS: positive m/z: 1123,5633. Phổ UV (MeOH), λmax, nm: 240. Phổ IR (MeOH), νmax, cm-1: 3423, 2924, 1741, 1635, 1067, 1039. Phổ 13C NMR (125 MHz, pyridine-d5,  ppm): 38,6 (C-1), 26,4 (C-2), 89,3 (C- 3), 39,5 (C-4), 55,7 (C-5), 18,4 (C-6), 33,1 (C-7), 39,9 (C-8), 48,0 (C-9), 36,9 (C-10), 23,7 (C-11), 122,9 (C-12), 144,1 (C-13), 42,1 (C-14), 28,2 (C-15), 23,3 (C-16), 47,0 (C-17), 41,7 (C-18), 46,1 (C-19), 30,7 (C-20), 34,0 (C-21), 32,5 (C-22), 28,0 (C-23), 16,8 (C-24), 15,5 (C-25), 17,4 (C-26), 26,1 (C-27), 176,4 (C-28), 33,1 (C-29), 23,6 (C- 30), 107,0 (C-1), 75,7 (C-2), 82,0 (C-3), 71,4 (C-4), 77,1 (C-5), 170,7 (C-6), 52,1 48 (OMe), 102,9 (C-1), 72,5 (C-2), 72,7 (C-3), 74,1 (C-4), 69,8 (C-5), 18,6 (C-6), 95,4 (C-1), 74,2 (C-2), 77,1 (C-3), 77,9 (C-4), 77,9 (C-5), 61,0 (C-6), 102,7 (C-1), 72,5 (C-2), 72,7 (C-3), 73,9 (C-4), 70,4 (C-5), 18,5 (C-6). Phổ 1H NMR (500 MHz, pyridine-d5,  ppm): 3,26 (1H, dd, J = 4,0 và 11,5 Hz, H-3), 5,38 (1H, br s, H-12), 3,16 (1H, d, J = 13,0 Hz, H-18), 1,21 (3H, s, H-23), 0,91 (3H, s, H-24), 0,78 (3H, s, H-25), 1,04 (3H, s, H-26), 1,24 (3H, s, H-27), 0,90 (3H, s, H-29), 0,87 (3H, s, H-30), 4,86 (1H, d, J = 7,5 Hz, H-1), 4,03-4,07 (1H, m, H-2), 4,37-4,42 (1H, m, H-3), 4,37-4,42 (1H, m, H-4), 4,48-4,54 (1H, m, H-5), 3,76 (OMe), 6,28 (1H, br s, H-1), 4,73 (1H, d, J = 1,5 Hz, H-2), 4,48-4,54 (1H, m, H-3), 4,30-4,34 (1H, m, H-4), 5,06 (1H, m, H-5), 1,68 (3H, d, J = 6,5 Hz, H-6), 6,20 (1H, d, J = 8,0 Hz, H-1), 4,10-4,14 (1H, m, H-2), 4,18-4,22 (1H, m, H-3), 4,48-4,54 (1H, m, H-4), 3,78 (1H, d, J = 9,5 Hz, H-5), 4,18-4,22 (1H, m, H-6a), 4,03-4,07 (1H, m, H-6b), 5,87 (1H, br s, H-1), 4,63 (1H, d, J = 1,5 Hz, H-2), 4,48-4,54 (1H, m, H-3), 4,30-4,34 (1H, m, H-4), 4,89-4,93 (1H, m, H-5), 1,66 (3H, d, J = 6,5 Hz, H-6). 3.3.11. Scheffleraside A (SS21, chất mới) Dạng bột, màu trắng. ሾαሿୈଶହ-17,0 (c 0,10, MeOH). Phổ HR-ESI-MS: positive m/z: 1109,5533, 1131,5492, negative m/z: 1085,5521. Phổ UV (MeOH), λmax, nm: 206 và 220. Phổ IR (MeOH), νmax, cm-1: 3418, 2927, 1726, 1615, 1075, 1030. Phổ 13C NMR (125 MHz, pyridine-d5,  ppm): 38,6 (C-1), 26,4 (C-2), 89,1 (C- 3), 39,4 (C-4), 55,6 (C-5), 18,4 (C-6), 33,1 (C-7), 39,8 (C-8), 47,9 (C-9), 36,8 (C-10), 23,7 (C-11), 122,9 (C-12), 144,1 (C-13), 42,0 (C-14), 28,2 (C-15), 23,3 (C-16), 47,0 (C-17), 41,7 (C-18), 46,1 (C-19), 30,7 (C-20), 34,0 (C-21), 32,5 (C-22), 28,1 (C-23), 16,9 (C-24), 15,4 (C-25), 17,4 (C-26), 26,0 (C-27), 176,4 (C-28), 33,1 (C-29), 23,6 (C- 30), 106,8 (C-1), 75,9 (C-2), 82,1 (C-3), 72,0 (C-4), 76,9 (C-5), 102,5 (C-1), 72,5 (C-2), 72,6 (C-3), 74,1 (C-4), 69,6 (C-5), 18,6 (C-6), 95,3 (C-1), 74,2 (C-2), 77,0 (C-3), 77,8 (C-4), 77,8 (C-5), 60,9 (C-6), 102,6 (C-1), 72,5 (C-2), 72,7 (C-3), 73,8 (C-4), 70,3 (C-5), 18,4 (C-6). Phổ 1H NMR (500 MHz, pyridine-d5,  ppm): 3,26 (1H, br d, J = 7,5 Hz, H-3), 5,38 (1H, br s, H-12), 3,15 (1H, br d, J = 10,0 Hz, H-18), 1,21 (3H, s, H-23), 0,92 (3H, s, H-24), 0,77 (3H, s, H-25), 1,03 (3H, s, H-26), 1,24 (3H, s, H-27), 0,89 (3H, s, H-29), 49 0,86 (3H, s, H-30), 4,86 (1H, d, J = 6,5 Hz, H-1), 4,00-4,06 (1H, m, H-2), 4,37-4,38 (1H, m, H-3), 4,26-4,34 (1H, m, H-4), 4,37-4,38 (1H, m, H-5), 6,28 (1H, br s, H-1), 4,71 (1H, br s, H-2), 4,56 (1H, d, J = 8,0 Hz, H-3), 4,26-4,34 (1H, m, H-4), 5,06 (1H, m, H-5), 1,68 (3H, d, J = 5,0 Hz, H-6), 6,18 (1H, d, J = 8,0 Hz, H-1), 4,09- 4,13 (1H, m, H-2), 4,16-4,20 (1H, m, H-3), 4,42-4,52 (1H, m, H-4), 3,76 (1H, d, J = 9,5 Hz, H-5), 4,16-4,20 (1H, m, H-6a), 4,00-4,06 (1H, m, H-6b), 5,85 (1H, br s, H-1), 4,63 (1H, br s, H-2), 4,42-4,52 (1H, m, H-3), 4,26-4,34 (1H, m, H-4), 4,85-4,89 (1H, m, H-5), 1,65 (3H, d, J = 6,0 Hz, H-6). 3.3.12. 3-O--D-glucopyranosylbetulin (SS10) Dạng bột, màu trắng. Phổ HR-ESI-MS: positive m/z: 627,4205. Phổ 13C NMR (125 MHz, pyridine-d5,  ppm): 38,5 (C-1), 26,8 (C-2), 89,2 (C- 3), 38,8 (C-4), 55,3 (C-5), 17,7 (C-6), 34,0 (C-7), 40,5 (C-8), 50,0 (C-9), 36,3 (C-10), 20,4 (C-11), 25,1 (C-12), 36,9 (C-13), 42,3 (C-14), 25,9 (C-15), 29,3 (C-16), 47,5 (C- 17), 48,5 (C-18), 47,5 (C-19), 150,7 (C-20), 29,6 (C-21), 33,9 (C-22), 27,5 (C-23), 16,2 (C-24), 15,6 (C-25), 15,5 (C-26), 14,3 (C-27), 58,9 (C-28), 109,1 (C-29), 18,7 (C- 30), 105,5 (C-1), 74,5 (C-2), 77,0 (C-3), 70,6 (C-4), 76,8 (C-5), 61,6 (C-6). Phổ 1H NMR (500 MHz, pyridine-d5,  ppm): 3,49 (1H, dd, J = 4,0 và 11,5 Hz, H-3), 1,36 (3H, s, H-23), 1,08 (3H, s, H-24), 0,84 (3H, s, H-25), 1,02 (3H, s, H-26), 1,02 (3H, s, H-27), 4,05-4,17 (1H, m, H28a) 3,67 (1H, d, J = 11,5 Hz, H28b), 4,92 (1H, br s, H29a), 4,85 (1H, br s, H29b), 1,85 (3H, s, H-30), 5,00 (1H, d, J = 8,0 Hz, H- 1), 4,05-4,17 (1H, m, H-2), 4,33 (1H, t, J = 9,5 Hz, H-3), 4,05-4,17 (1H, m, H-4), 4,05-4,17 (1H, m, H-5), 4,53 (1H, br d, J = 11,0 Hz, H-6a), 4,34-4,37 (1H, m, H-6b). 3.3.13. Scheffleraside D (SS11, chất mới) Dạng bột, màu trắng. ሾαሿୈଶହ-32,0 (c 0,15, MeOH). Phổ HR-ESI-MS: positive m/z: 643,4160. Phổ UV (MeOH), λmax, nm: 193. Phổ IR (MeOH), νmax, cm-1: 3450, 2940, 2870, 1641, 1078, 1040. Phổ 13C NMR (125 MHz, CD3OD,  ppm): 39,8 (C-1), 28,2 (C-2), 90,9 (C-3), 40,8 (C-4), 61,9 (C-5), 69,0 (C-6), 47,0 (C-7), 43,2 (C-8), 51,2 (C-9), 40,0 (C-10), 21,9 (C-11), 26,5 (C-12), 38,3 (C-13), 43,9 (C-14), 26,9 (C-15), 30,3 (C-16), 49,0 (C- 17), 50,0 (C-18), 49,0 (C-19), 151,8 (C-20), 30,8 (C-21), 35,1 (C-22), 31,3 (C-23), 50 16,8 (C-24), 17,7 (C-25), 18,0 (C-26), 15,2 (C-27), 60,4 (C-28), 110,3 (C-29), 19,3 (C- 30), 106,9 (C-1), 75,7 (C-2), 78,3 (C-3), 71,7 (C-4), 77,7 (C-5), 62,8 (C-6). Phổ 1H NMR (500 MHz, CD3OD,  ppm): 3,13 (1H, dd, J = 4,5 và 11,5 Hz, H- 3), 0,91 (1H, d, J = 11,0 Hz, H-5), 3,99 (1H, ddd, J = 4,0, 10,5 và 11,0 Hz, H-6), 1,57 (1H, dd, J = 11,5 và 12,0 Hz, H-7α), 1,62-1,68 (1H, m, H-7β), 1,38 (3H, s, H-23), 1,05 (3H, s, H-24), 0,94 (3H, s, H-25), 1,16 (3H, s, H-26), 1,06 (3H, s, H-27), 3,75 (1H, d, J = 11,5 Hz, H-28a), 3,29-3,31 (1H, m, H-28b), 4,70 (1H, br s, H-29a), 4,59 (1H, br s, H-29b), 1,71 (3H, s, H-30), 4,33 (1H, d, J = 7,5 Hz, H-1), 3,22 (1H, t, J = 8,5 Hz, H- 2), 3,56 (1H, t, J = 8,5 Hz, H-3), 3,29-3,31 (1H, m, H-4), 3,27 (1H, m, H-5), 3,85 (1H, dd, J = 2,0 và 12,0 Hz, H-6a), 3,67 (1H, dd, J = 5,5 và 12,0 Hz, H-6b). 3.3.14. 2β,12β-dihydroxygibberellin (SS01, chất mới) Tinh thể hình kim, màu vàng nhạt. ሾαሿୈଶହ+141 (c 0,35, MeOH). Phổ HR-ESI-MS: negative m/z: 363,1818. Phổ UV (MeOH), λmax, nm: 204. Phổ IR (MeOH), νmax, cm-1: 3434,2921,1714, 1660,1025. Phổ 13C NMR (125 MHz, CD3OD,  ppm): 49,0 (C-1), 66,0 (C-2), 48,0 (C-3), 45,0 (C-4), 59,8 (C-5), 50,5 (C-6), 179,8 (C-7), 52,0 (C-8), 58,8 (C-9), 45,9 (C-10), 27,9 (C-11), 73,4 (C-12), 49,0 (C-13), 43,7 (C-14), 47,0 (C-15), 149,4 (C-16), 109,5 (C-17), 28,5 (C-18), 180,2 (C-19), 16,3 (C-20). Phổ 1H NMR (500 MHz, CD3OD,  ppm): 1,99 (1H, dd, J = 4,0 và 13,0 Hz, H- 1α), 0,87 (1H, t, J = 11,5 Hz, H-1β), 4,19 (1H, m, H-2), 2,45 (1H, dd, J = 4,0 và 13,0 Hz, H-3α), 1,04 (1H, t, J = 12,0 Hz, H-3β), 2,01 (1H, d, J = 12,0 Hz, H-5), 3,43 (1H, d, J = 11,5 Hz, H-6), 1,61 (1H, d, J = 10,5 Hz, H-9), 1,77-1,83 (1H, m, H-11α), 1,50 (1H, m, H-11β), 3,80 (1H, ddd, J = 3,5, 7,5 và 10,5 Hz, H-12), 2,60 (1H, br s, H-13), 1,77-1,83 (2H, m, H-14), 2,24 (1H, d, J = 15,5 Hz, H-15a), 2,18 (1H, d, J = 15,5 Hz, H-15b), 5,04 (1H, s, H-17a), 5,00 (1H, br s, H-17b), 1,20 (3H, br s, H-18), 0,91 (3H, s, H-20). 3.3.15. 3-O-β-D-glucuronopyranosylkaempferol (SS03) Dạng bột, màu vàng. Phổ HR-ESI-MS: positive m/z: 463,0871, 485,0697, 507,0505. 51 Phổ 13C NMR (125 MHz, DMSO-d6,  ppm): 156,3 (C-2), 133,2 (C-3), 177,4 (C-4), 161,1 (C-5), 98,8 (C-6), 164,4 (C-7), 93,7 (C-8), 156,4 (C-9), 103,8 (C-10), 120,6 (C-1), 131,0 (C-2, C-6), 115,1 (C-3, C-5), 160,1 (C-4), 101,2 (C-1), 73,9 (C-2), 76,1 (C-3), 71,7 (C-4), 75,1 (C-5), 171,0 (C-6). Phổ 1H NMR (500 MHz, DMSO-d6,  ppm): 12,48 (1H, s, OH-5), 6,18 (1H, d, J = 1,5 Hz, H-6), 6,40 (1H, d, J = 2,0 Hz, H-8), 8,03 (2H, d, J = 9,0 Hz, H-2, H-6), 6,87 (2H, d, J = 8,5 Hz, H-3, H-5), 5,40 (1H, d, J = 7,5 Hz, H-1), 3,20-3,26 (2H, m, H-2, H-3), 3,25-3,30 (1H, m, H-4), 3,38-3,42 (1H, m, H-5). 3.3.16. trans-Tiliroside (SS02) Dạng bột, màu vàng. Phổ HR-ESI-MS: positive m/z: 617,1289. Phổ 13C NMR (125 MHz, DMSO-d6,  ppm): 156,4 (C-2), 133,1 (C-3), 177,4 (C-4), 161,3 (C-5), 98,8 (C-6), 164,2 (C-7), 93,7 (C-8), 156,4 (C-9), 103,9 (C-10), 120,8 (C-1), 130,8 (C-2, C-6), 115,1 (C-3, C-5), 160,0 (C-4), 101,0 (C-1), 74,1 (C-2), 76,2 (C-3), 70,0 (C-4), 74,2 (C-5), 63,0 (C-6), 124,9 (C-1), 130,1 (C- 2, C-6), 115,7 (C-3, C-5), 159,8 (C-4), 144,6 (C-7), 113,6 (C-8), 166,1 (C-9). Phổ 1H NMR (500 MHz, DMSO-d6,  ppm): 12,56 (1H, s, OH-5), 6,14 (1H, d, J = 2,0 Hz, H-6), 6,38 (1H, d, J = 2,0 Hz, H-8), 7,98 (2H, d, J = 8,5 Hz, H-2, H-6), 6,85 (2H, d, J = 9,0 Hz, H-3, H-5), 5,44 (1H, d, J = 7,0 Hz, H-1), 3,17-3,29 (3H, m, H-2, H-3, H-4), 3,36 (1H, m, H-5), 4,26 (1H, dd, J = 1,5 và 11,5 Hz, H-6a), 4,03 (1H, dd, J = 6,5 và 12,0 Hz, H-6b), 7,36 (2H, d, J = 8,5 Hz, H-2, H-6), 6,78 (2H, d, J = 8,5 Hz, H-3, H-5), 7,34 (1H, d, J = 16,0 Hz, H-7), 6,10 (1H, d, J = 16,0 Hz, H-8). 3.3.17. Acid 5-p-trans-coumaroylquinic (SS04) Dạng bột, màu trắng. Phổ HR-ESI-MS: positive m/z: 361,0891. Phổ 13C NMR (125 MHz, CD3OD,  ppm): 76,1 (C-1), 38,8 (C-2), 71,3 (C-3), 73,5 (C-4), 72,0 (C-5), 38,2 (C-6), 177,0 (C-7), 127,3 (C-1), 131,2 (C-2,C-6), 116,8 (C-3,C-5), 161,3 (C-4), 146,7 (C-7), 115,4 (C-8), 168,6 (C-9). Phổ 1H NMR (500 MHz, CD3OD,  ppm): 7,48 (2H, d, J = 8,5 Hz, H-2, H-6), 6,83 (2H, d, J = 8,5 Hz, H-3, H-5), 7,64 (1H, d, J = 16,0 Hz, H-7), 6,33 (1H, d, J = 52 16,0 Hz, H-8), 5,36 (1H, td, J = 4,5 và 9,5 Hz, H-5), 4,19 (1H, td, J = 3,0 và 5,5 Hz, H-3), 3,75 (1H, dd, J = 3,5 và 8,5 Hz, H-4), 2,25 (1H, ddd, J = 2,0, 4,5 và 13,5 Hz, H- 2a), 2,22 (1H, dd, J = 3,5 và 14,0 Hz, H-6a), 2,05-2,09 (1H, m, H-6b), 2,10-2,13 (1H, m, H-2b). 3.3.18. 3-O--D-glucopyranosylstigmasterol (SS07) Dạng bột, màu trắng. Phổ HR-ESI-MS: positive m/z: 597,4117. Phổ 13C NMR (125 MHz, CDCl3 & CD3OD,  ppm): 37,5 (C-1), 29,8 (C-2), 79,4 (C-3), 39,9 (C-4), 140,6 (C-5), 122,3 (C-6), 32,1 (C-7), 32,1 (C-8), 50,5 (C-9), 37,0 (C-10), 21,3 (C-11), 38,9 (C-12), 42,4 (C-13), 57,1 (C-14), 24,5 (C-15), 29,1 (C-16), 56,2 (C-17), 12,3 (C-18), 19,5 (C-19), 40,7 (C-20), 21,3 (C-21), 138,6 (C-22), 129,5 (C-23), 51,5 (C-24), 32,1 (C-25), 21,2 (C-26), 19,1 (C-27), 25,6 (C-28), 12,3 (C-29), 101,4 (C-1), 73,8 (C-2), 76,7 (C-3), 70,5 (C-4), 76,4 (C-5), 62,1 (C-6). Phổ 1H NMR (500 MHz, CDCl3 & CD3OD,  ppm): 3,57-3,61 (1H, m, H-3), 5,36 (1H, br d, J = 5,0 Hz, H-6), 0,71 (3H, s, H-18), 1,02 (3H, s, H-19), 1,02 (3H, d, J = 7,5 Hz, H-21), 5,16 (1H, dd, J = 8,5 và 15,0 Hz, H-22), 5,02 (1H, dd, J = 8,5 và 15,0 Hz, H-23), 0,85 (3H, d, J = 6,5 Hz, H-26), 0,80 (3H, d, J = 7,0 Hz, H-27), 0,81 (3H, d, J = 7,5 Hz, H-29), 4,40 (1H, d, J = 7,5 Hz, H-1), 3,23 (1H, t, J = 8,5 Hz, H-2), 3,30 (1H, m, H-3), 3,40-3,44 (1H, m, H-4, H-5), 3,84 (1H, dd, J = 2,5 và 12,0 Hz, H-6a), 3,75 (1H, dd, J = 5,0 và 12,0 Hz, H-6b). 3.3.19. Muối natri của (2S)-1,2-di-O-palmitoyl-3-O-α-D-(6- sulfo)quinovopyranosylglycerol (SS09) Dạng bột, màu trắng. ሾαሿୈଶହ+9,0o (c 0,20, MeOH). Phổ HR-ESI-MS: positive m/z: 817,5118, 839,4950. Phổ HR-ESI-MS/MS: positive m/z: 239,2358, 313,2704, 551,4974, 591,4894. Phổ GC-MS (MW, RT, %): 270 (19,747, 85,76%), 256 (20,155, 1,77%), 284 (20,761, 3,20%), 296 (21,525, 1,00%), 298 (21,765, 8,27%). Phổ 13C NMR (125 MHz, CD3OD,  ppm): 64,3 (C-1), 71,7 (C-2), 67,1 (C-3), 100,0 (C-1), 73,5 (C-2), 74,9 (C-3), 75,0 (C-4), 69,9 (C-5), 54,3 (C-6),175,0 (C- 1), 175,2 (C-1), 35,0 (C-2), 35,2 (C-2), 26,0 (C-3, C-3), 30,2-30,8 (C-4C- 13, C-4C-13), 33,1 (C-14, C-14), 23,7 (C-15, C-15), 14,4 (C-16, C-16). 53 Phổ 1H NMR (500 MHz, CD3OD,  ppm): 4,54 (1H, dd, J = 3,0 và 12,0 Hz, H- 1a), 4,20 (1H, dd, J = 7,0 và 12,0 Hz, H-1b), 5,34 (1H, m, H-2), 4,13 (1H, dd, J = 5,5 và 11,0 Hz, H-3a), 3,59 (1H, dd, J = 6,0 và 10,5 Hz, H-3b), 4,78 (1H, d, J = 3,5 Hz, H-1), 3,42 (1H, dd, J = 3,5 và 9,5 Hz, H-2), 3,65 (1H, t, J = 9,5 Hz, H-3), 3,10 (1H, t, J = 9,5 Hz, H-4), 4,09 (1H, t, J = 9,5 Hz, H-5), 3,36 (1H, dd, J = 2,0 và 14,5 Hz, H- 6a), 2,94 (1H, dd, J = 9,5 và 14,5 Hz, H-6b), 2,32-2,39 (4H, m, H-2, H-2), 1,60- 1,63 (4H, m, H-3, H-3), 1,22-1,38 (48H, br s, H-4H-15, H-4H-15), 0,92 (6H, t, J = 7,0 Hz, H-16, H-16). 3.3.20. sn-1-monoacylglycerol và sn-1,2-diacylglycerol (SS05) Dạng bột, màu trắng. Phổ GC-MS (MW, RT, %): 268 (22,696, 13,53%), 270 (22,800, 76,40%), 296 (26,251, 4,83%), 298 (26,742, 5,24%). Phổ 13C-NMR (125 MHz, CDCl3,  ppm): 174,1, 173,8, 135,5, 130,0, 121,2, 67,0 (C-1), 71,3 (C-2), 62,8 (C-3), 63,0 (C-1), 70,8 (C-2), 64,2 (C-3), 34,5 (C-α), 34,4 (C-α), 25,2 (C-β), 25,1 (C-β), 32,1 (C-ω3), 22,8 (C-ω2), 14,1 (C-ω1). Phổ 1H-NMR (500 MHz, CDCl3,  ppm): 3,99 (2H, m, H-1), 3,85 (1H, m, H-2), 3,65 (2H, m, H-3), 4,37-4,39 (1H, m, H-1a’), 4,15-4,18 (1H, m, H-1b’), 5,22 (1H, m, H- 2’), 3,99 (2H, m, H-3’), 2,28-2,33 (4H, m, H-α), 1,60-1,61 (4H, m, H-β), 1,27 (50H, br s), 0,88 (6H, t, J = 6,5 Hz, H-ω1). 3.3.21. 1-O-β-D-glucopyranosyl-(2S,3S,4R,8E)-2-[(2’R)-2-hydroxypalmitoylamino]- octadec-8-en-1,3,4-triol và 1-O-β-D-glucopyranosyl-(2S,3S,4R,8Z)-2-[(2’R)- 2-hydroxypalmitoylamino]-octadec-8-en-1,3,4-triol (SS08) Dạng bột, màu trắng. ሾαሿୈଶହ+11,0o (c 0,20, MeOH). Phổ HR-ESI-MS: positive m/z: 570,5067, 732,5595, 754,5417. Phổ HR-ESI-MS/MS: positive m/z: 280,2626, 455,3090, 552,4967. Phổ 13C-NMR (125 MHz, pyridine-d5,  ppm): 70,4 (C-1), 51,7 (C-2), 75,9 (C- 3), 72,4 (C-4), 27,6 (C-7Z), 32,1 (C-7E), 130,4 (C-8Z), 130,8 (C-8E), 130,2 (C-9Z), 130,6 (C-9E), 27,9 (C-10Z), 33,0 (C-10E), 22,9 (C17), 14,3 (C-18), 175,7 (C-1), 72,4 (C-2), 35,6 (C-3), 32,1 (C-14), 22,9 (C-15), 14,3 (C-16), 105,6 (C-1), 75,1 (C-2), 78,4 (C-3), 71,5 (C-4), 78,5 (C-5), 62,6 (C-6). 54 Phổ 1H-NMR (500 MHz, pyridine-d5,  ppm): 8,53 (1H, d, J = 9,5 Hz, NH), 4,69 (1H, dd, J = 6,5 và 10,5 Hz, H-1a), 4,50 (1H, dd, J = 4,0 và 10,5 Hz, H-1b), 5,26 (1H, m, H-2), 4,26-4,29 (1H, m, H-3), 4,15-4,21 (1H, m, H-4), 5,43-5,54 (2H, m, H-8,H-9), 0,85 (3H, t, J = 6,5 Hz, H-18), 4,55-4,57 (1H, m, H-2), 0,85 (3H, t, J = 6,5 Hz, H-16), 4,93 (1H, d, J = 8,0 Hz, H-1), 4,00 (1H, t, J = 8,0 Hz, H-2), 4,15-4,21 (2H, m, H-3, H-4), 3,85 (1H, m, H-5), 4,56 (1H, dd, J = 2,0 và 11,5 Hz, H-6a), 4,32 (1H, dd, J = 5,0 và 11,5 Hz, H-6b). 3.3.22. Thủy phân xác định các đơn vị đường của SS11, SS16, SS20, SS21 Thủy phân các hợp chất triterpenoid saponin mới (SS11, SS16, SS20, SS21) dựa theo phương pháp của nhóm tác giả Haddad M.[31]. Mỗi saponin (2 mg) cho phản ứng với CH3COOH 2 N (5 mL) trong 2 h ở 100 oC. Sau đó, đem dung dịch sau thủy