. 66 - 7. 62 (m, 1H), 7. 55 - 7. 49 (m, 4H), 7. 47 - 7. 44 (m, 1H), 7. 41 (t,J= 7. 8Hz, 2H), 7. 36 (t,J= 7. 8Hz, 2H), 7. 28 - 7. 25 (m, 2H), 6. 92 (d,J= 3. 7Hz, 1H), 6. 16 (d,J =2. 4Hz, 1H), 6. 08 (dd,J= 10. 7, 3. 3Hz, 1H), 5. 97 (dd,J= 10. 7, 3. 7Hz, 1H), 4. 87 (t,J= 6. 4Hz, 1H), 4. 62 (dd,J= 11. 4, 6. 9Hz, 1H), 4. 44 (dd,J= 11.5,6. 0Hz, 1H).
[0054] 實施例2 :表雄酮糖基化衍生物的制備
[0055]
[0056] 【式（A-4-1)所示化合物】將A-3 (889mg,I. 2mmol)、CH21 (200mg, 0? 6mmol)溶 解在無水二氯甲烷（20mL)中，加入三氟甲磺酸三甲基硅脂（0. 24mL，0. 3mmol)，室溫反 應6小時。反應完全后，減壓除去溶劑，加入水（30mL)，乙酸乙酯（30mLX3)萃取，合并 有機相，無水硫酸鈉干燥，硅膠柱層析（PE:EA= 3 :1)純化，得到如式（A-4-1)所示的白 色固體（442mg，81 %)。1HNMR(400MHz，CDC13)S8.04(d，J= 8.3Hz，2H)，7.98(d，J= 7. 2Hz, 2H), 7. 92 (d,J= 8. 2Hz, 2H), 7. 84 (d,J= 8. 2Hz, 2H), 7. 56 - 7. 49 (m, 3H), 7. 40 (dd,J =16. 9, 9. 2Hz, 5H), 7. 35 (t,J= 7. 7Hz, 2H), 7. 27 (t,J= 7. 7Hz, 2H), 5. 94 (t,J =9. 6Hz, 1H), 5. 66 (t,J= 9. 6Hz, 1H), 5. 25 (d,J = 4. 5Hz, 1H), 4. 92 (d, J = 7. 5Hz, 1H), 4. 62 - 4. 56 (m, 2H), 4. 18 - 4. 15 (m, 1H), 3. 59 - 3. 49 (m, 1H), 3. 02 (dd, J = 15.I, 6. 3Hz, 1H), 2. 61 (dd,J= 15. 0, 12. 0Hz, 1H), 2. 48 (d,J= 12. 5Hz, 1H), 2. 23- 2. 15m, 3H), 2. 08 - 2. 02 (m, 1H),I. 97 (d,J= 12. 2Hz, 1H),L95 -I. 84 (m, 1H),I. 10 (s, 3H), 0. 97 (s, 3H).
[0057] 【式（B-4-1)所示化合物】按照化合物A-4-1的合成方法以化合物 B-3(889mg，1.2mmol)和CH21(200mg，0. 6mmol)為原料，得到如式（B-4-1)所示的白色固體 (42611^78^)0 4^^(40010^,0)(:13)5 8.11-8.04(111,411),8.00 - 7.95(111,211),7.86-7. 81 (m, 2H), 7. 61 - 7. 56 (m, 2H), 7. 51 (t, J = 7. 4Hz, 1H), 7. 45 - 7. 35 (m, 7H), 7. 26 (dd, J =4. 8, 2. 7Hz, 2H), 6. 05(t, J = 10. 0Hz, 1H), 5. 93 (dd, J = 10.I, 3. 3Hz, 1H), 5. 64 (dd, J =3. 2,I. 8Hz, 1H), 5. 25(d, J =I. 4Hz, 1H), 4. 70 (dd, J = 11.8,2.1Hz,lH),4.54-4. 51 (m, 1H), 4. 47 (dd, J = 11. 9, 5. 1Hz, 1H), 3. 74 - 3. 65 (m, 1H), 3. 03 (dd, J = 15. 5, 6. 3Hz, 1H), 2. 61 (dd, J = 15. 5, 12. 0Hz, 1H) , 2. 48 - 2. 40 (m, 1H), 2. 23 - 2. 17 (m, 1H),I. 96 (d, J = 10. 5Hz, 1H),L60 -I. 49 (m, 3H),L36 -I. 21 (m, 4H),I. 10 (s, 3H) ,0. 93 (s, 3H).
[0058] 【式（C-4-1)所示化合物】按照化合物A-4-1的合成方法以化合物C-3和CH21 為原料，得到如式（C-4-1)所示的白色固體（89% )。1H NMR(400MHz，CDC13) 5 8. 13(dd, J =8. 3, I. 3Hz, 2H), 7. 95 (dd, J = 8. 3, I. 2Hz, 2H), 7. 81 (dd, J = 8. 3, I. 2Hz, 2H), 7. 63 -7. 58 (m, 1H), 7. 55 - 7. 47 (m, 3H), 7. 45 - 7. 34 (m, 3H), 7. 29 - 7. 24 (m, 3H), 5. 85 (dd, J = 10.I, 3. 4Hz, 1H), 5. 68 (t,J= 10. 0Hz, 1H), 5. 63 (dd,J= 3. 4,I. 8Hz, 1H), 5. 19 (t,J=4. 3Hz, 1H), 4. 33 - 4. 23 (m, 1H), 3. 66 - 3. 55 (m, 1H), 3. 11 - 3.OO(m, 1H), 2. 65 (dd,J =15. 5, 11. 9Hz, 1H), 2. 54 - 2. 43 (m, 2H), 2. 39 (dd,J= 17. 8, 6. 7Hz, 1H), 2. 27 - 2. 21 (m, 1H), 2. 14 - 2. 43 (m, 1H), 2. 04 -I. 92 (m, 3H),I. 86 - I. 70 (m, 5H),I. 38 (d, J= 6. 3Hz, 3H),I. 16 (s, 3H),I. 14 (s, 3H).
[0059] 【式（D-4-1)所示化合物】按照化合物A-4-1的合成方法以化合物D-3和CH21 為原料，得到如式（D-4-1)所示的白色固體（421mg，77 %)。1HNMR(400MHz,CDCl3) 8 8. 11 (d,J= 7. 3Hz, 2H), 8. 03(d,J= 7. 2Hz, 2H), 7. 97 (d,J= 7. 3Hz, 2H), 7. 79 (d,J =7. 3Hz, 2H), 7. 62 (t,J= 7. 4Hz, 1H), 7. 56 (dd,J= 13.I, 5. 7Hz, 1H), 7. 53- 7. 46 (m, 3H), 7. 44 - 7. 38 (m, 5H), 7. 27 - 7. 22 (m, 2H), 5. 98 (d,J= 2. 9Hz, 1H), 5. 78 (dd,J =10. 3, 8.0Hz, 1H), 5.60 (dd,J= 10. 4,3.4Hz, 1H), 4.92 (d,J= 8.0Hz, 1H), 4.69 (dd,J =11. 2, 6. 9Hz, 1H), 4. 42(dd,J= 11. 2, 6. 5Hz, 1H), 4. 33 (t,J= 6. 7Hz, 1H), 3. 62- 3. 52 (m, 1H), 3. 02 (dd,J= 15. 5, 6. 3Hz, 1H), 2. 61 (dd,J= 15. 5, 12. 0Hz, 1H), 2. 48 (d,J =12. 5Hz, 1H), 2. 26 - 2. 16 (m, 3H), 2. 08 -I. 98 (m, 2H), I. 93 -I. 86 (m, 1H),I. 81 - 1. 78 (m, 2H),I. 76 -I. 59 (m, 5H),I. 11 (s, 3H),I. 01 (s, 3H).
[0060] 【式（A-5-1)所示化合物】將A-4-l(420mg，0.46mmol)溶解在無水四氫呋喃 (IOmL)和甲醇（IOmL)混合溶劑中，加入甲醇鈉（497mg，9. 2mmol)，室溫反應6小時。反應 完全后，除去溶劑，加入稀鹽酸調(diào)pH呈弱酸性，乙酸乙酯（30mLX3)萃取，無水硫酸鈉干 燥，硅膠柱層析（DCM:MeOH= 5 :1)分離純化，得到如式（A-5-1)所示的白色固體（200mg， 88 % ) 〇1HNMR(400MHz,DMS〇-d6) 8 4. 89 (d,J= 4. 5Hz, 1H), 4. 87 - 4. 83 (m, 2H), 4. 43 (t,J =5. 8Hz, 1H), 4. 23 (d,J= 7. 8Hz, 1H), 3. 67 - 3. 63 (m, 1H), 3. 45 - 3. 37 (m, 2H), 3. 16 (t,J =4. 2Hz, 1H), 3. 11 (dd,J= 8. 6, 4. 6Hz, 1H), 3. 06 (d,J= 5. 3Hz, 2H), 3. 02 (d,J= 5. 9Hz, 1H)，2. 92 - 2. 87 (m, 1H)，2. 71 - 2. 61 (m, 1H)，2. 31 - 2. 23 (m, 1H)，2. 14 (dd,J= 17. 2, 11. 1Hz, 1H),I. 76 (dd,J= 17. 2, 6. 6Hz, 3H),I. 72 -I. 62 (m, 5H),I. 55 -I. 37 (m, 2H), 1.01(s, 3H),0. 85 (s, 3H).
[0061] 【式（B-5-1)所示化合物】按照化合物A-5-1的合成方法以化合物 B-4-1 (420mg, 0? 46mmol)為原料，得到如式（B-5-1)所示的白色固體（198mg， 87 % ) 〇1HNMR(400MHz,CDCl3) 8 5. 03 (s, 1H), 3. 99 (s, 2H), 3. 94 (s, 2H) , 3. 75(d,J= 14. 3Hz, 1H), 3. 61 (d,J= 11. 1Hz, 1H), 3. 55 (s, 1H) , 2. 99 (dd,J= 15. 4, 6.OHz, 1H), 2. 58 (dd,J= 15.I, 12. 2Hz, 1H) , 2. 50 - 2. 36 (m, 1H), 2. 20 - 2. 14 (m, 1H),I. 89 (d,J= 8. 7Hz, 1H),I. 82 (d,J= 10. 9Hz, 1H),I. 74 (s, 4H),I. 55 (d,J= 7. 3Hz, 2H),L43 -I. 26 (m, 5H),I. 08 (s, 3H), 0. 89 (s, 3H)
[0062] 【式（C-5-1)所示化合物】按照化合物A-5-1的合成方法以化合物C-4-1 為原料，得到如式（C-5-1)所示的白色固體（86 %)。1HNMR(400MHz,CDCl3) 84.95(s,lH),3.89(s,lH),3.83-3.77 (m,lH),3.76-3.71(m,lH),3.62- 3. 51 (m, 1H) , 3. 49 - 3. 43 (m, 1H) , 3. 01 (dd,J= 15. 5, 6. 3Hz, 1H) , 2. 59 (dd,J =15.3, 12.IHz,IH), 2. 48-2. 39 (m, 1H),2. 24-2. 17 (m, 1H), 1.82(d,J =I1. 1Hz, 2H) , 1. 77 (d,J= 12. 3Hz,4H), 1.66(s,4H),I. 54(dd,J= 17. 3, 10. 8Hz, 2H),L31 (d,J= 6. 1Hz, 3H),L27 -I. 23 (m, 1H),I. 09 (s, 3H), 0. 90 (s, 3H).
[0063] 【式（D-5-1)所示化合物】按照化合物A-5-1的合成方法以化合物D-4-1 為原料，得到如式（D-5-1)所示的白色固體（87 % )。1HNMR(400MHz，DMS0-d6) 8 4. 78 (d,J= 3....