二氢-β-沉香呋喃型倍半萜类化合物、其制法和用图_3

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4),2.11(m, 1H,H-6a),2. 29 (m, 1H, H-6b),2. 11 (m, 1H, H-7),2. 27 (m, 1H, H-8a),2. 11 (m, 1H, H-8b) ,5. 24 (d,1H,J = 6. 8Hz,H-9),1. 40 (s,3H,H-12),1. 22 (s,3H,H-13),1. 30 (d,3H,J = 7.0Hz,H-14),5.03,4.49(d,each 1H,J = 12.6Hz,H-15);13C NMR(CDC13)S Ac0-1[20.9 (q),170. 0(s)],Ac〇-15[21. 6(q),170. 8(s)],Cin〇-2and Cin〇-9[118. 2x 2(d),128. 4x 4(d), 129. Ox 4(d), 130. 5x 2(d), 134. 5x 2 (s), 145. 3 (d), 145. 6 (d), 166. 2x 2(s)],71 .4 (d, C-l), 70. 8 (d, C-2) ,31.1 (t, C-3), 39. 4 (d, C-4), 86. 7 (s, C-5), 36. 4 (t, C-6), 43. 7 (d, C-7), 34. 1 (t, C-8), 69. 6 (d, C-9), 50. 6(s, C-10), 82. 3(s, C-ll), 24. 3 (q, C-12), 30 .3(q, C-13),19. 1(q, C-14), 65. 9(t,C-15) ;HRT0FMS m/z 653. 2739[M+Na]+ (calcd for C37H4209Na, 653. 2727).
[0138] CB-4C :白色无定形粉末; [a ] f +21:0. 0 (c 0? 10,CHC13); UV A nax (Methanol) 218 (3. 9)nm, 279(4. 0)nm ;IR(KBr) v nax 1745, 1711, 1637, 1450, 13 67, 1234, 1165, 1016, 767cm S 4 匪R(CDC13) S 1. 81 (3H, s, AcO-1), 2. 13(3H, s, Ac〇-6 ),Cin〇-2and Cin〇-9 [7.67 (d,lH,J = 16.5Hz),7.63 (d,lH,J = 16.5Hz),7.53 (m,4H ),7.38(m,6H),6.38(d,lH,J = 16.5Hz),6.37 (d,lH,J = 16.5Hz) ],5.65 (d,lH,J = 3. 9Hz, H-l), 5. 70 (dd, 1H, J = 7. 8, 3. 9Hz, H-2), 2. 44 (m, 1H, H-3a), 1. 89 (dd, 1H, J = 15. 0, 3. 0Hz, H-3b), 2. 37 (t, 1H, J = 7. 5Hz, H-4), 5. 42 (s, 1H, H-6), 2. 23 (brs, 1H, H-7), 2. 23 (m, 1H, H-8a), 2. 16 (m, 1H, H-8b), 4. 77 (d, 1H, J = 7. OHz, H-9), 1. 42 (s, 3H, H-12), 1. 41 (s, 3 H, H-13), 1. 27 (d, 3H, J = 7. OHz, H-14), 1. 52 (s, 3H, H-15) ;13C NMR (CDC13) S Ac〇-l [20. 9 (q ),170.2 (s)],Ac〇-6 [21.6 (q), 170.3 (s)],Cin〇-2and Cin〇-9 [118. 1(d), 118.4(d), 128. 2x 2 (d), 128. 4x 2 (d), 129. Ox 2 (d), 129. lx 2 (d), 130. 5x 2 (d), 134. 4 (s), 134. 5 (s), 145. 1 ( d), 145. 7 (d), 166. 2 (s), 166. 3 (s) ], 71. 1 (d, C-l), 70. 4 (d, C-2), 31. 2 (t, C-3), 33. 9 (d, C-4),89. 6 (s, C-5),79. 3 (d, C-6),48. 9 (d, C-7),31. 6 (t, C-8),72. 9 (d, C-9),49. 9 (s, C-10), 83. 0 (s, C-l 1),26. 1 (q, C-12),30. 8 (q, C-13),18. 9 (q, C-14),20. 6 (q, C-15) ;HRTOFMS m/z 653. 2742[M+Na] + (calcd for C37H4209Na, 653. 2727).
[0139] CB-4S :白色无定形粉末;[a ]f +87. 0 (c 〇? l〇,CHCl3); UV 入 nax (Methanol) 218 (4. 2) nm,223(4. l)nm,276(4. 2) nm ;IR(KBr) Vnax 1742, 1713, 1639, 1 392, 1366, 1280, 1227, 1100, 1015, 709cm S 虫 NMR(CDC13) S 1. 62 (3H, s, Ac〇-l), 2. 13 (3H, s ,Ac〇-6), Bz〇-9and Cin〇-2 [8. 06 (d, 2H, J = 7. 4Hz), 7. 63 (d, 1H, J = 16. 1Hz), 7. 56 (t, 1H, J =7. 0Hz), 7. 51 (m, 2H), 7. 44 (t, 2H), 7. 39 (m, 3H), 6. 37 (d, 1H, J = 16. 1Hz) ], 5. 65 (d, 1H, J =3. 2Hz, H-l) ,5.73 (dd,lH,J = 7. 5,3.2Hz, H-2) ,2.49 (m,lH,H-3a), 1.90 (dd,lH,J = 15. 1,3. 3Hz, H-3b),2. 40 (t, 1H, J = 7. 7Hz, H-4),5. 46 (s, 1H, H-6),2. 26 (t, 1H, J = 7. 0Hz, H-7),2. 20 (m,1H,H-8a),2. 16 (m,1H,H-8b),4. 99 (d,1H,J = 6. 9Hz,H-9),1. 43 (s,3H,H-12) ,1. 42 (s,3H,H-13),1. 27 (d,3H,J = 7. 2Hz,H-14),1. 55 (s,3H,H-15) ;13C NMR (CDC13) S AcO -1[20. 6(q),169. 8(s)],Ac〇-15[21. 6(q),170. 3(s)],Bz〇-9and Cin〇-2[118. 3(d),128. 3x 2(d),128.4x 2(d),129. lx 2(d),129.6 (s),130. 2x 2(d),130. 6(d),133. 4(d),134.4 (s) ,145. 1 (d),165. 7 (s),166. 3 (s) ],71. 4 (d,C-l),70. 3 (d,C-2),31. 7 (t,C-3),33. 9 (d,C-4) ,89. 7 (s,C-5),79. 4 (d,C-6),49. 0 (d,C-7),31. 2 (t,C-8),73. 2 (d,C-9),50. 0 (s,C-10),8 3. 1 (s,C-ll),26. 2 (q,C-12),30. 8 (q,C-13),18. 9 (q,C-14),20. 7 (q,C-15) ;HRTOFMS m/z 627. 2588[M+Na] + (calcd for C35H4009Na, 627. 2570).
[0140] CB-2H:白色无定形粉末;[a ]f +72. 3 (c 〇? 〇8,CHCl3); UV 入 _(Methanol)218(4. l)nm,223(4. l)nm,277(4. 2)nm ;IR(KBr) v_ 1747, 1718, 164 匪R(pyridine-d5) S 1.97(3H,s,Ac〇-l ),Hex〇-2 [2. 36 (t, 2H, J = 7. 2Hz) ,2.11 (m, 2H), 1. 66 (m, 2H), 1. 27 (m, 2H), 0. 85 (t, 3H, J =7.1Hz) ],Cin〇-9 [8.03 (d,lH,J = 16.0Hz) ,7.56 (m,2H), 7.32 (m,3H), 6.78 (d,lH,J = 16. 0Hz) ],5. 96 (d, 1H, J = 3. 4Hz, H-l),6. 00 (dd, 1H, J = 7. 4, 3. 4Hz, H-2),2. 49 (ddd, 1H,J =15. 0, 6. 8, 3. 2Hz,H-3a),1. 77 (dd,1H,J = 15. 0, 3. 2Hz,H-3b),1. 99 (m,1H,H-4),2. 0 6 (m,1H,H-6a),2. 02 (m,1H,H-6b),1. 92 (m,1H,H-7),2. 21 (m,1H,H-8a),2. 14 (m,1H,H-8 b),5. 13 (d,1H,J = 6. 8Hz,H-9),1. 55 (s,3H,H-12),1. 24 (s,3H,H-13),1. 29 (d,3H,J = 7.0Hz,H-14),1.46(s,3H,H-15) ;13C NMR(pyridine-d5)S Ac0-l[21.3(q),170.7(s)],H ex〇-2[14. 5(q), 23. 0(t), 25. 4 (t), 32. 0(t), 35. 2 (t), 173. 4 (s) ], Cin〇-9 [119. 7(d), 12 9. lx 2 (d), 129. 7x2 (d) ,131.1 (d), 136. 3 (s), 145. 6 (d), 166. 6 (s) ], 72. 2 (d, C-l), 70. 9 (d, C-2), 31. 7 (t, C-3), 40. 3 (d, C-4), 88. 1 (s, C-5), 36. 5 (t, C-6), 44. 5 (d, C-7), 31. 8 (t ,C-8),74. 3 (d,C-9),47. 9 (s,C-10),83. 0 (s,C-ll),24. 9 (q,C-12),30. 9 (q,C-13),19. 8 (q, C-14), 20. 6(q, C-15) ;HRTOFMS m/z563. 2996 [M+Na]+ (calcd for C32H4407Na, 563. 2985).
[0141] CB-4R:白色无定形粉末; [a ] f +l〇〇. 2 (c 0.07,CHC13); UV A nax (Methanol) 206 (4. 4) nm, 218(4. 4) nm, 279(4. 6)nm ;IR(KBr) v nax 1746, 1719, 1 643, 1452, 1365, 1223, 1162, 1134, 1012, 879, 767, 710cm S 4 匪R(CDC13) S 1. 78 (3H, s,Ac〇-l),2. 16 (3H,s,Ac〇-15),But〇-2 [2. 33 (m,2H),1. 69 (m,2H),0? 96 (t,3H,J = 7. 0Hz) ], Cin〇-9 [7. 67 (d, 1H, J = 16. 0Hz), 7. 54 (m, 2H), 7. 38 (m, 3H), 6. 36 (d, 1H, J = 16. 0Hz) ], 5. 68 (d, 1H, J = 3. 2Hz, H-l), 5. 56 (dd, 1H, J = 7. 3, 3. 2Hz, H-2), 2. 46 (ddd, 1H, J =15. 0, 6. 9, 3. 0Hz, H-3a), 1. 75 (dd, 1H, J = 15. 0, 3. 0Hz, H-3b), 1. 92 (t, 1H, J = 6. 9Hz, H-4), 2. 06 (m, 1H, H-6a), 2. 33 (m, 1H, H-6b), 2. 11 (m, 1H, H-7), 2. 24 (m, 1H, H-8a), 2. 08 (m, 1 H, H-8b), 5. 17 (d, 1H, J = 7. 0Hz, H-9), 1. 38 (s, 3H, H-12), 1. 20 (s, 3H, H-13), 1. 26 (d, 3H, J =7. 0Hz, H-14),4. 84, 4. 40 (d, each 1H, J = 12. 7Hz, H-15) ;13C NMR(CDC13) S Ac〇-l [20. 9 (q),169. 8 (s) ],Ac〇-15 [21. 6 (q),170. 8 (s) ],But〇-2 [13. 8 (q),18. 5 (t),36. 8 (t),172. 9 (s) ], Cin〇-9 [118. 2 (d), 128. 4x 2 (d), 129. Ox 2 (d), 130. 5 (d), 134. 5 (s), 145. 5 (d), 166. 2 (s) ],71. 4 (d, C-l),70. 1 (d, C-2),31. 2 (t, C-3),39. 5 (d, C-4),86. 7 (s, C-5),36. 4 (t, C-6 ),43. 7 (d,C-7),34. 2 (t,C-8),69. 6 (d,C-9),50. 6 (s,C-10),82. 2 (s,C-l 1),24. 3 (q,C-12) ,30. 3(q, C-13), 18. 9(q, C-14), 65. 8(t, C-15) ;HRTOFMS m/z 563. 2734[M+Na]+ (calcd for C32H4209Na, 593. 2727).
[0142] 本发明中其它化合物的波谱数据如下:
[0143] PE-11:MF:C33H3S07, Mff:546 ;白色无定形粉末;ES頂S m/z 547. 3[M+H]+; 4 NMR(CDC13,400MHz)S Ac〇-l[1.62(3H,s)],Cin〇-6[6.47,7.71(each lH,d,J = 16.1Hz ),7. 42 (3H, m), 7. 55(2H, m)], Bz〇-9[7. 45(2H, brt, J = 6. 8Hz), 7. 57 (1H, brt, J = 6. 8Hz), 8. 08 (2H, brd, J = 6. 8Hz) ], 5. 52 (dd, 1H, J = 12. 2, 4. 4Hz, H-l), L 53 (m, 1H, H-2a), 1. 90 (ddd, 1H, J = 12. 2, 8. 3, 3. 9Hz, H-2b), 1. 46 (m, 1H, m, H-3a), 2. 26 (m, 1H, H-3b) ,2. 37 (q, 1H, J = 7. 3Hz, H-4), 5. 47 (brs, 1H, H-6), 2. 32 (m, 1H, H-7), 2. 48 (ddd, 2H, J = 16. 6, 6. 8, 3. 3Hz, H-8), 5. 02 (d, 1H, J = 6. 8Hz, H-9), 1. 43 (s, 3H, H-12), 1. 45 (s, 3H, H-13), I. 03 (d,3H,J = 7. 3Hz,H-14),1. 37 (s,3H,H-15);
[0144] PE-13:MF:C31H360S,Mff:536 ;白色无定形粉末;ES頂S m/z 559. 2[M+Na]+; :H NMR(CDC13, 400MHz) 8 Ac〇-6 [2. 13 (3H, s) ], Bz〇-8, Bz〇-9 [8. 10 (2H, d, J = 7. 5Hz), 8. 03 (2H, d, J = 7. 5Hz), 7. 87 (2H, d, J = 7. 5Hz), 7. 54 (m, 2H), 7. 50 (m, 3H), 7. 44 (t, 2H, J = 7. 3Hz), 7. 25 (2H, t, J = 7. 3Hz) ], 4. 14 (dd, 1H, J = 10. 7, 5. 1Hz, H-l), 1. 57, 1. 94 (m ,each 1H, H-2), 1. 49, 2. 29 (m, each 1H, H-3), 2. 40 (m, 1H, H-4), 6. 19 (brs, 1H, H-6), 2. 57 (m ,1H, H-7), 5. 83 (ddd, 1H,
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