一种黄酮类化合物5-o-糖苷的制备方法_3

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), 5. 71 (d, J = 7. 2Hz, 1H), 4. 60 (dd, J = 3. 3, 12. 2Hz, 1H), 4. 49 (dd, J =4. 8, 12. 2Hz, 1H), 4. 22-4. 17 (m, 1H), 1. 00 (s, 9H), 0. 99 (s, 9H), 0. 94 (s, 9H) ,0.73( s, 9H), 0. 223 (s, 3H), 0. 218 (s, 3H), 0. 21 (s, 3H), 0. 20 (s, 6H), 0. 197 (s, 3H), 01 (s, 3H),-0· 02 (s, 3H) ;13C NMR(100MHz, CDC13) δ 172. 6, 166. 0, 165. 8, 165. 2, 165. 1,159. 3, 157 .5, 155. 9, 149. 6, 148. 6, 146. 6, 137. 7, 133. 0, 130. 1, 129. 83, 129. 80, 129. 7, 129. 6, 128. 35 ,128. 25, 128. 1, 123. 0, 121. 4, 120. 7, 110. 9, 109. 9, 103. 9, 100. 0, 77. 3, 77. 0, 76. 7, 73. 0, 7 2. 4, 72. 0, 69. 6, 62. 9, 25. 9, 25. 7, 25. 5, 18. 7, 18. 5, 18. 4, 18. 2, -4. 0, -4. 07, -4. 1, -4. 21,-4. 25, -4. 41, -4. 44 ;HRMS (ESI) calcd for C73H92016Si4Na+: 1359. 5355, Found: 1359. 5361〇
[0079]实施例5
[0080] 3, 7, 3',4' -四-0-叔丁基二甲基硅基-5-0- (2, 3, 4-三-0-苯甲酰基-a -L-鼠李 糖)槲皮素糖苷的制备
[0081]
[0082] 步骤1 :全苯甲酰基保护鼠李糖给体的制备:
[0083]
[0084] 氮气保护下,将异头位裸露的全Bz保护的鼠李糖(5g, 10. 5mmol)及邻炔基苯甲 酸(2.3g,12.6mmol)溶于干燥的DCM(12mL)中,然后向体系中加入EDCI(2.3g,11.6mmol), DMAP(1. 2g,11. 6mmol)和DIPEA(3. 5ml,19. 5mmol),并于室温下搅拌 3h,TLC跟踪至反应结 束。将反应体系减压浓缩粗产品,然后柱层析得鼠李糖炔酯给体(6.lg,93% );
[0085] 步骤2 :合成方法如实施例4步骤2所示;
[0086] 步骤3 :3, 7, 3',4' -四-0-叔丁基二甲基硅基-5-0-(2, 3, 4-三-0-苯甲酰 基-a-L-鼠李糖)槲皮素糖苷的制备
[0087]
[0088]氮气保护下,将全苯甲酰基保护的鼠李糖给体(97mg,0. 15mmol)和3, 7, 3',4' -四 叔丁基二甲基娃基槲皮素(76mg, 0.lmmol)溶于干燥的DCM(3mL)中,反应体系在室 温下搅拌30min后,加入Ph3PAuNTf2 (22mg, 0. 03mmol),室温搅拌直至反应完全。反 应体系减压浓缩后得粗产品,柱层析纯化得目标产物(120mg,99%)。[]f= 7.7 (c1. 9,CHC13)NMR(400MHz,CDC13)δ8. 17 (d,J= 7. 32Hz, 2H),8. 04 (d,J= 7. 4Hz, 2H),7. 88 (d,J= 7. 32Hz, 2H),7. 64 (t,J= 7. 36Hz, 1H),7. 56-7. 24 (m, 10H),6. 92(d ,J= 8. 4Hz, 1H),6. 58 (dd,J= 2, 13. 4Hz, 1H),6. 52 (dd,J= 3. 4, 10. 4Hz, 1H),6. 12-6. 11(m ,1H),5. 89(s,1H),5. 81 (t,J= 10. 0Hz, 1H),4. 57-4. 50(m,1H),1. 33 (d,J=6. 2Hz, 3H),1. 0 2(s,9H),L〇l (s,18H),0. 83(s,9H),0. 33(s,3H),0. 29(s,6H),0. 28(s,3H),0. 24(s,6H),0. 23 (s, 6H);13CNMR(100MHz,CDC13)δ172. 8, 166. 0, 165. 5, 164. 9, 159. 7, 157. 9, 155. 6, 149. 2, 148. 6, 146. 6, 138. Ο, 133. 4, 133. 2, 130. 0, 129. 9, 129. 7, 129. 6, 129. 4, 128. 6, 128. 3, 128.1, 123. 0, 121. 3, 120. 7, 110. 3, 105. 2, 102. 4, 96. 1, 77. 3, 77. 2, 77. 0, 76. 7, 72. 0, 70. 7, 69. 7. 68. 2, 29. 7, 26. 0, 25. 9, 25. 6, 19. 0, 18. 6, 18. 5, 18. 3, 17. 7, -3. 5, -3. 6, -4. 06, -4. 07, -4. 2, -4. 3, -4. 4 ;HRMS (ESI) calcd for C66H89014Si4Na+: 1217. 5324, Found: 1217. 5314〇
[0089]实施例6
[0090] 3, 7, 4' -三-0-苄基-5-0-(2, 3, 4-三-0-苯甲酰基-a -L-鼠李糖)山奈酚糖苷 的制备
[0091]
[0092]步骤1 :合成方法如实施例5步骤1所示;
[0093]步骤2 :合成方法如实施例2步骤2所示;
[0094]步骤3 :3, 7, 4' -三-0-苄基-5-0-(2, 3, 4-三-0-苯甲酰基-a -L-鼠李糖)槲皮 素糖苷的制备:
[0095]
[0096]合成方法如实施例1步骤3所示:96 %,[ ]$ = 22.3 (C〇·64, CHC13); ? NMR(400MHz,CDCl3)S8.16(d,J = 7.5Hz,2H),8.05(d,J = 7.5Hz,2H),7.99(d,J = 8. 4Hz, 2H), 7. 89 (d, J = 7. 5Hz, 2H), 7. 51-7. 35 (m, 24H), 7. 03 (d, J = 8. 4Hz, 2H), 6. 80 (s, 1H ),6. 72 (s, 1H),6. 42 (d, J = 10. 3Hz, 2H),6. 13 (s, 1H),5. 92 (s, 1H),5. 84 (t, J = 9. 8Hz, 1H), 5.21-5.10(m,6H),4.61-4.57(m,lH),1.36(d,J = 5.9Hz,3H) ;13C NMR(100MHz,CDC13) δ173 .2, 166. 0, 165. 5, 165. 2, 162. 4, 160. 2, 158. 4, 156. 2, 153. 7, 133. 5, 133. 2, 130. 2, 130. 0, 12 9. 9, 129. 7, 129. 1, 128. 7, 128. 65, 128. 58, 128. 4, 128. 2, 128. 1, 127. 9, 127. 51, 127. 46, 123.5, 114. 6, 110. 7, 101. 4, 96. 6, 96. 5, 77. 3, 77. 0, 76. 7, 74. 0, 71. 9, 70. 7, 70. 5, 70. 0, 69. 9, 6 8.4, 17.7 ;HRMS (ESI) calcd for C63H50013Na+: 1037. 3144, Found: 1037. 3140〇
[0097]实施例7
[0098]3, 7, 4' -三-0-己酰基-5-0-(2, 3, 4-三-0-苯甲酰基-a -L-鼠李糖)山奈酚糖 苷的制备
[0099]
[0100] 步骤1 :合成方法如实施例5步骤1所示;
[0101] 步骤2 :合成方法如实施例3步骤2所示;
[0102] 步骤3 :3, 7, 4' -三-0-己酰基-5-0-(2, 3, 4-三-0-苯甲酰基-a -L-鼠李糖)山 奈酚糖苷的制备:
[0103]
[0104]合成方法如实施例1步骤3所示:82 %,[ = 15,9 (c 0. 9, CHC13) JH 匪R (400MHz,CDC13) δ 8.15 (d,J = 7·4Ηζ,2Η) ,8.04 (d,J = 7·5Ηζ,2Η) ,7.90-7. 86 (m,4H), 7. 52-7. 24(m, 11H), 7. 10(d, J = 1. 8Hz, 1H), 6. 94 (d, J = 1. 8Hz, 1H), 6. 36 (dd, J =3. 32, 10. 12Hz, 1H), 6. 05 (s, 1H), 5. 89 (s, 1H), 5. 81 (t, J = 9. 96, 1H), 4. 44-4. 37 (m ,1H), 2. 68-2. 57 (m, 6H), 1. 80-1. 75 (m, 6H), 1. 41-1. 22 (m, 14H), 0. 96-0. 83 (m, 9H) ;13C NMR(100MHz, CDC13) δ 171. 7, 171. 0, 170. 98, 170. 0, 165. 9, 165. 4, 165. 0, 157. 6, 156. 1,154 .6, 153. 6, 152. 8, 134. 3, 133. 5, 133. 2, 132. 9, 129. 9, 3, 129. 90, 129. 7, 129. 52, 129. 46, 129 .33, 129. 26, 128. 6, 128. 3, 128. 2, 127. 1, 121. 9, 113. 1, 105. 7, 105. 4, 96. 3, 77. 3, 77. 2, 77. 0, 76. 7, 71. 7, 70. 6, 69. 7, 68. 3, 34. 3, 33. 9, 31. 19, 31. 15, 31. 14, 24. 5, 24. 41, 24. 37, 22. 3, 22. 2, 13. 9, 13. 83, 13. 81 ;HRMS(ESI)calcd for C60H62016Na+:1061. 3930,Found:1061. 3930。
[0105]实施例8
[0106] 3, 7,4'-三-0-叔丁基二甲基硅基-5-0-(2, 3,4, 6-四-0-苯甲酰基-β-D-半乳 糖)山奈酚糖苷的制备
[0107]
[0108] 合成方法如实施例 1 所示:99 %,[ (6 = 47..6(c1.6,CHC13)JH MMR(400MHz,CDCl3)S8.13(d,J= 7.4Hz,2H),8.06(d,J= 7.3Hz,2H),7.94(d,J= 7. 4Hz, 2H), 7. 84 (d,J= 7. 3Hz, 2H), 7. 65-7. 24 (m, 14H), 6. 88 (d,J= 8. 4Hz, 1H), 6. 70 (d,J =2. 2Hz, 1H), 6. 58 (d,J= 2. 4Hz, 1H), 6. 25 (dd,J= 3. 4, 8. 4Hz, 1H), 4. 44-4. 40 (m, 2H), 1. 00 (s, 9H), 0. 99 (s, 9H), 0. 98 (s, 9H), 0. 72 (s, 9H), 0. 26 (s, 3H), 0. 256 (s, 3H), 0. 22 (s, 6H), 0 ? 20(s,6H),0.03(s,3H),-0.12(s,3H);13CNMR(100MHz,CDC13)S172.6,165.9,165.6,165. 3, 159. 4, 157. 6, 156. 3, 149. 6, 148. 6, 146. 6, 137. 7, 133. 21, 133. 18, 130. 1, 130. 08, 129. 8, 129. 7, 128. 6, 128. 4, 128. 36, 128. 3, 128. 1, 110. 8, 109. 3, 103. 7, 100. 6, 77. 3, 77. 0, 76
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