6, 21. 03, 20. 96, 20. 89, 20. 76.
[0170] 式（2-2)，產(chǎn)率為 84 %，結(jié)構(gòu)確證=1H 匪R(300MHz, CDCl3) 86.70(s, 1H),5. 16(s, 1H),5. 10(d,J = 4. 2Hz, 1H) , 4. 52 (dd, J = 9. 8, 3. 3Hz, 0. 5H), 4. 41 (dd, J = 9. 4, 2. 7Hz, 0. 5H), 4. 36 - 4. 19 (m, 2H) ,4.19- 4. 03 (m, 1H) , 4. 00 (d, J = 7. 5Hz, 0. 5H) , 3. 75 (d, J = 9.4Hz,0.5H),2.48- 2. 28 (m, 4H) , 2. 26 - 2. 03 (m, 13H) , I. 98 (dd, J = I 2. 3, 6. I Hz, 2H) , 1. 9 I -I. 56 (m, 2H), I. 54 - I. 18 (m, 11H). 13C NMR (75MHz, CDCl3) S 213. 58, 213. 47, 170. 91，170. 84 ,169. 84, 169. 60, 169. 54, 169. 38, 169. 13, 168. 99, 130. 88, 128. 82, 78. 56, 77. 73, 76. 30, 65 .72, 65. 54, 65. 36, 62. 91, 62. 74, 62. 28, 60. 44, 50. 73, 41. 95, 33. 90, 33. 22, 30. 56, 30. 00, 2 9. 59, 29. 33, 29. 27, 28. 02, 27. 13, 26. 23, 26. 12, 24. 82, 22. 78, 20. 97, 20. 89, 20. 83, 20. 69.
[0171] 式（卜2)，產(chǎn)率為 89 %，結(jié)構(gòu)確證=1H NMR(300MHz, Pyr) 8 6. 54 (s, 1H), 6. 03 (br, 4H), 4. 69 (t, J = 6. 4Hz, 1H), 4. 42 (t, J = 6. 6Hz, 1H), 4. 32 -4. 16 (m, 2H), 3. 87 (s, 1H), 3. 59 (d, J = 4. 5Hz, 1H), 2. 42 - 2. 29 (m, 2H), 2. 20 (dd, J = 12. 9, 5. 1Hz, 2H), 2. 11 (d, J = 4. 2Hz, 2H), 2. 06 - I. 95 (m, 1H), I. 81 (s, 1H) ,1.79-1.69(m, 2H), 1.66 - 1.43(m, 2H), 1.43- I. 06 (m, 8H). 13C NMR(75MHz, Pyr) 8 198.81, 145. 18 ,139. 78, 83. 21, 79. 30, 65. 03, 62. 85, 62. 58, 38. 84, 34. 54, 30. 05, 29. 99, 29. 73, 29. 73, 28. 99, 27. 13, 26. 15, 23. 48.
[0172] 實(shí)施例2
[0173] 本實(shí)施例用于說明本發(fā)明的小構(gòu)樹堿類化合物及其制備方法。
[0174]
[0175] 根據(jù)對比例1所述的方法，所不同的是，采用式（3-3)所示的硝酮代替式（3-1)所 示的；其中，
[0176] 式（11-3)，產(chǎn)率為 94 %，結(jié)構(gòu)確證：111匪1?(3001抱，0)(：13)85.51- 5. 26 (m, 2H) , 4. 59 - 4. 26 (m, 3H) , 3. 97 (d, J = 9. 9Hz, 0. 5H) , 3. 75 (d, J = 10. 4Hz, 0. 5H), 2. 47 - 2. 19 (m, 5H), 2. 18 - I. 93 (m, 12H), I. 91 - I. 56 (m, 5H), I. 56 - 1. 11 (m, 13H). 13C NMR (75MHz, CDCl3) S 213. 33, 213. 26, 170. 07, 169. 76, 169. 64, 169. 45, 16 9. 39, 77. 40, 75. 03, 73. 97, 69. 91，68. 77, 63. 43, 63. 25, 62. 49, 60. 63, 56. 54, 54. 96, 50. 58， 41. 81，34. 41，33. 79, 33. 71，31. 04, 29. 48, 29. 43, 29. 22, 29. 16, 29. 12, 27. 93, 26. 95, 26. 18 ，26. 05, 24. 68, 22. 85, 21. 95, 20. 86, 20. 74, 20. 58, 20. 42, 20. 30.
[0177] 式（2-3)，產(chǎn)率為 83 %，結(jié)構(gòu)確證：? NMR(300MHz，CDC13) S6.69(t, J = 3. 9Hz, 1H), 5. 52 - 5. 27 (m, 2H), 4. 59 - 4. 41 (m, 1H), 4. 38 - 4. 25 (m, 2H), 3. 97 (dd, J = 10. 2, 2. 5Hz, 0. 5H), 3. 73 (d, J = 10. 6Hz, 0. 5H), 2. 45 - 2. 30 (m, 4H), 2. 22 (s, 2H) ,2.19- 2. 09 (m, 6H) , 2. 09 - 2. 01 (m, 6H) , 2. 00 - I. 92 (m, 2H) , I. 52 - I. 10 (m, 12H) . 13C NMR (75MHz, CDCl3) S 199. 59, 170. 32, 170. 20, 169. 92, 169. 74, 169. 58, 144. 97, 144. 88, 139 .88, 130. 91, 128. 83, 75. 11, 74. 02, 71. 77, 70. 00, 68. 83, 63. 54, 63. 35, 62. 57, 60. 76, 56. 60 ,55. 01, 38. 60, 34. 55, 31. 18, 29. 48, 29. 42, 29. 24, 28. 54, 28. 45, 26. 33, 26. 20, 26. 04, 23. I 6, 22. 98, 22. 07, 20. 99, 20. 87, 20. 71, 20. 55, 20. 43, 19. 15.
[0178] 式（1-3)，產(chǎn)率為 77 %，結(jié)構(gòu)確證=1H NMR (300MHz, MeOD) S 6.86 (t, J = 4. 1Hz, 1H), 4. 13 (t, J = 3. 6Hz, 1H), 3. 95 - 3. 72 (m, 3H), 3. 44 (d, J = 3. 0Hz, 1H), 3. 19 (dd, J =13. I, 8. 2Hz, 1H), 2. 50 - 2. 32 (m, 3H), 2. 24 - 2. 07 (m, 2H), 2. 03 - I. 90 (m, 1H) ,1.88- 1. 64 (m, 2H), L 62 - I. 18 (m, 12H). 13C NMR (75MHz, MeOD) 8 202. 03, 148. 07, 140. 75, 78. 54, 7 2. 87, 62. 36, 62. 05, 61. 06, 39. 49, 34. 03, 30. 65, 30. 63, 30. 44, 30. 41, 29. 92, 27. 86, 27. 07, 24. 30.
[0179] 實(shí)施例3
[0180] 本實(shí)施例用于說明本發(fā)明的小構(gòu)樹堿類化合物及其制備方法。
[0181]
[0182] 根據(jù)對比例1所述的方法，所不同的是，采用式（3-4)所示的硝酮代替式（3-1)所 示的；其中，
[0183] 式（11-4)，產(chǎn)率為 76 %，結(jié)構(gòu)確證：111匪1?(3001抱，0)(：13)55.51- 5. 24 (m, 2H),4. 61 - 4. 22 (m, 3H),4. 04 - 3. 90 (m, 0. 5H),3. 73 (d, J = 10. 6Hz, 0. 5H) ,2.44- 2. 18 (m, 5H), 2. 18 - 1. 91 (m, 12H), 1. 90 - 1. 56 (m, 5H), 1. 54 - 1. 10 (m, 13H). 13C NMR (75MHz, CDCl3) S 213. 50, 170. 25, 170. 15, 169. 90, 169. 86, 169. 70, 169. 54, 169. 48, 130 ? 87, 128. 80, 75. 12, 74. 03, 69. 99, 68. 83, 65. 51，63. 54, 63. 35, 62. 57, 60. 75, 56. 63, 55. 03， 50. 70, 41. 90, 34. 53, 33. 86, 33. 77, 31. 16, 30. 54, 29. 57, 29. 30, 29. 21，28. 00, 27. 05, 26. 28 ,26. 15, 24. 75, 22. 94, 22. 03, 20. 94, 20. 82, 20. 66, 20. 50, 20. 38.
[0184] 式（2-4)，產(chǎn)率為 78 %，結(jié)構(gòu)確證匪R(300MHz, CDCl3) 8 6. 70 (d, J = 3. 6Hz, 1H),5. 52 - 5. 24 (m, 2H),4. 60 - 4. 21 (m, 3H),4. 04 - 3. 68 (m, 1H) , 2. 77 (s, IH) , 2. 49 - 2. 28 (m, 3H) , 2. 2 5 - I. 90 (m, 15H) , 1.84-1. 43 (m, 2H), I. 43 - I. 17 (m, 12H). 13C NMR (75MHz, CDCl3) S 199. 47, 177. 93, 170. 21，170. 17，170. 13, 169. 83, 169. 76, 169. 51，169. 46, 144. 97, 144. 89, 139. 75, 75. 03, 73. 96, 69. 92, 68 .78, 63. 45, 63. 28, 62. 50, 60. 65, 56. 52, 54. 95, 38. 51，34. 43, 31. 06, 29. 59, 29. 39, 29. 34, 2 9. 14, 29. 10, 28. 44, 28. 37, 26. 23, 26. 10, 25. 97, 23. 09, 22. 89, 22. 00, 20. 91, 20. 79, 20. 63, 20. 47, 20. 35.
[0185] 式（1-4)，產(chǎn)率為 89%，結(jié)構(gòu)確證：? NMR(300MHz,Pyr) S 6. 54(s, 1H), 6. 46(br, 4 H),4. 65 (s, 1H),4. 52 (d, J = 7. 4Hz, 1H),4. 39 (d, J = 12. 7Hz, 2H),4. 21 (s, 1H),3. 88 (d, J =4. 9Hz, 1H),2. 42 - 2. 30 (m, 1H),2. 28 - 2. 16 (m, 1H),2. 15 - I. 96 (m, 4H),I. 85 -I. 65 (m, 3H)，I. 56 (s, 2H)，I. 43 - I. 08 (m, 9H)?13C NMR (75MHz, Pyr) S 199. 14, 145. 49, 140. 2 5, 78. 86, 72. 99, 63. 14, 62. 09, 61. 02, 39. 29, 33. 53, 30. 42, 30. 29, 30. 16, 30. 08, 29. 41, 27. 75, 26. 57, 23. 91.
[0186] 實(shí)施例4
[0187]本實(shí)施例用于說明本發(fā)明的小構(gòu)樹堿類化合物及其制備方法。
[0188]
[0189] 根據(jù)實(shí)施例1所述的方法，所不同的是，采用5-溴-1-戊烯代替7-溴-1-庚烯來 制備格氏試劑；其中，
[0190] 式（11-5)，產(chǎn)率為 90 %，結(jié)構(gòu)確證：? 匪R(300MHz, CDCl3) 8 4. 93 (s, 1H), 4. 86 (s, 1H), 4. 29 (d, J = 7. 5Hz, 0. 5H), 4. 19 (d, J = 7. 7Hz, 0. 5H) ,4.08- 3. 95 (m, 1H) , 3. 94 - 3. 81 (m, 1H) , 3. 76 (d, J = 8. 9Hz, 0. 5H) , 3. 57 (d, J = 10. 4Hz, 0. 5H), 2. 20 - I. 73 (m, 16H), 1. 72 - 1. 34 (m, 5H), 1. 33 - 0. 84 (m, 10H). 13C NMR(75MHz, CDCl3) S 212. 57, 212. 41, 170. 25, 170. 16, 169. 30, 169. 03, 168. 93, 168. 81, 168 .58, 168. 47, 78. 05, 77. 59, 77. 35, 77. 23, 77. 16, 77. 03, 76. 73, 75. 82, 65. 13, 64. 81, 62. 49, 62. 29, 61. 76, 59. 88, 50. 07, 41. 47, 33. 56, 33. 49, 33. 41, 32. 61, 29. 39, 28. 93, 28. 82, 27. 56 ,26. 44, 25. 55, 24. 41, 24. 34, 22. 27, 20. 43, 20. 37, 20. 29, 20. 16.
[0191] 式（2-5)，產(chǎn)率為 74 %，結(jié)構(gòu)確證=1H 匪R(300MHz, CDCl3) 86.71(s, 1H),5. 16(s, lH),5.09(d,J = 3. 3Hz, 1H) , 4. 53 (dd, J = 9. 7, 3. 3Hz, 0. 5H) , 4. 41 (d, J = 8.0Hz,0.5H),4.33-4.19(m,lH),4.18- 4. 03 (m, 1H) , 3. 99 (d, J = 9. 6Hz, 0. 5H) , 3. 75 (d, J = 9. 9Hz, 0. 5H) , 2. 45 - 2. 29 (m, 4H), 2. 23 - 2. 04 (m, 14H), 2. 04 - I. 91 (m, 2H), I. 90 - I. 56 (m, 1H), I. 55 -I. 24 (m, 7H) ? 13C NMR (75MHz, CDCl3) S 199. 47, 170. 94, 170. 87, 169. 90, 169. 67, 169. 57, 169 .44, 169. 17, 169. 04, 145. 15, 145. 01, 139. 86, 139. 76, 78. 67, 77. 80, 76. 40, 65. 76, 65. 42, 6 3. 01, 62. 85, 62. 35, 60. 52, 38. 62, 33. 22, 30. 00, 29. 52, 29. 48, 29. 15, 28. 58, 28. 45, 26. 11, 26. 06, 26. 01, 23. 21, 22. 84, 21. 04, 21. 01, 20. 94, 20. 88, 20. 74.
[0192] 式（1-5)，產(chǎn)率為 74 %，結(jié)構(gòu)確證=1H NMR (300MHz, MeOD) S