多酚黄酮类化合物及其制备方法和应用_3

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4" ' ),70.9(C-5" ' ),18.2(C-6" ' ),119.5(C-1" " ),108.1(C-2"", 6" " ),145.4(C-3" ",5" " ),138.2(C-4" " ),165.0(C-7" " )·
[0063] 化合物12 :黄色粉末(甲醇)。盐酸-镁粉、Mo I i sh反应为阳性。1H-NMR (600MHz, DMS0-d6)SH:6.05(lH,br s,H-6),6.24(lH,br s,H-8),7.89(2H,d,J = 8.8Hz,H-2,, 6,),6.78(2H,d,J = 8.8Hz,H-3',5' ),5.57(lH,d,J = 8.0Hz,H-l" ),7.34(2H,d,J = 8.4Hz,H-2",,6",),6.70(2H,d,J = 8.4Hz,H-3",,5",),7.55(lH,d,J=16.0Hz, H-7" ' ),6.25(lH,d,J=16.0Hz,H-8" ' ).13C-NMR(150MHz,DMS0-d6)Sc:158.1(C-2), 134. 6 (C-3),178. 8 (C-4),162. 8 (C-5),100. 4 (C-6),165. 4 (C-7),94. 5 (C-8),158. 0 (C-9), 105.7(C-10),122.6(C-1' ),132.0(C-2',6' ),116.0(C-3',5' ),161.2(C-4'), 99.6(C-1" ),75.7(C-2" ),76.2(C-3" ),71.5(C-4" ),78.6(C-5" ),62.5(C-6"), 127.1(C-1" ' ),131.0(C-2" ' 6" ' ),116.6(C-3" ' 5" ' ),160.9(C-4"'), 146.6(C-7"' ),115.0(C-8"' ),168.1(C-9"' )·
[0064] 化合物13 :黄色粉末(甲醇)。盐酸-镁粉、Mo I i sh反应为阳性。1H NMR (400MHz, CD3OD) :6. 17(1H,d,J = 2. 1Hz,H-6),6· 33(1H,d,J = 2. 1Hz,H-8),7· 56(1H,d,J = 2.4Hz,H-2 ' ),6.72(lH,d,J = 9.0Hz,H-5 ' ),7.54(lH,m,H-6 ' ),5.19(lH,d, J = 7.5Hz,H-I " ),δ6·94(2Η,s,H-2 " ',6 " ' ).13C NMR(100MHz,CD3OD) :δ : 158. 3 (C-2),133. 2 (C-3),179. 3 (C-4),162. 8 (C-5),99. 9 (C-6),165. 8 (C-7),94. 9 (C-8), 159. 3(C-9),105. 6(C-10),123.0 (C-l' ),117. 2(C-2 ' ),145. 7(C-3' ),149. 7(C-4 '), 115.9(C-5' ),123.6(C-6' ),104.2(C-1" ),75.7(C-2" ),78.0(C-3" ),71.5(C-4"), 75.9(C-5" ),64.3(C-6" ),121.3(C-1" ' ),110.2(C-2" ',6" ' ),146.3(C-3"', 5" ' ),139.7(C-4" ' ),165.8(C-7" ' )·
[0065] 化合物14 :黄色粉末(甲醇)。盐酸-镁粉、Moiish反应为阳性。1H-Nmr^oomhz, DMS0-d6) δ h:6. 70(1H,br s,H-6),6. 70(1H,br s,H-8),8. 45(2H,d,J = 8. 4Hz, H-2,,6,),7.16(2H,d,J = 814Hz,H-3,,5,),5.26(lH,d,J = 7.6Hz,H-l"), 7. 08(1H,d,J = L 5Hz,H-2 " ,),6. 85 (1H,d,J = 8. 0Hz,H_5 " r ),6. 99 (1H, dd,J = 8. 0,1. 5Hz,H-6 " ,),7. 54 (1H,d,J = 16. 0Hz,H_7 " ,),6. 24 (1H,d, J = 16. OHz, H-8 ' ) .13C-匪R (150MHz,DMS0-d6) δ c: 157. I (C-2),133.6(03), 179. 2 (C-4),163. I (C-5),99. 9 (C-6),165. 9 (C-7),94. 2 (C-8),157. I (C-9),104. 8 (C-IO), 122.3(C-1' ),132.1(C-2',6' ),116.0(C-3',5' ),16L9(C-4' ),104.1(C-1"), 76.5(C-2" ),73.2(C-3" ),71.3(C-4" ),76.0(C-5" ),64.2(C-6" ),127.1(C-1"'), 131.8(C-2" ',6" ' ),116.1(C-3" ',5" ' ),161.9(C-4" ' ),145.0(C-7"'), 115. 2(C-8" ' ),167. 0(C-9" ' )·
[0066] 化合物15 :黄色粉末(甲醇)。盐酸-镁粉、Mo I i sh反应为阳性。1H-NMR (600MHz, DMS0-d6) δ Η:6· 70(1H,br s,Η-6),6· 71 (1H,br s,Η-8),8· 45 (2H,d,J = 8. 4Hz, H-2,,6,),7.16(2H,d,J = 8.4Hz,H-3,,5,),5.23(lH,d,J = 7.6Hz,H-l"), 7. 53(lH,d,J=16. 0Hz,H-7",),6. 24(lH,d,J=16. 0Hz,H-8",).6. 85(lH,d,J = 8.5Hz,H-5",),6.99(lH,dd,J = 8.5,2.5Hz,H-6",),7.07(lH,d,J = 2.5Hz, H-2 " ' ),3. 78 (3H,s,-OCH3)。13C-NMR(150MHz,DMS0-d6) δ c:157. 8 (C-2),133. 3 (C-3), 178. 7 (C-4),162. 8 (C-5),100. 0 (C-6),166. 0 (C-7),94. 7 (C-8),157. 7 (C-9),105. 2 (C-10), 121.9(01' ),131.9(C-2',6' ),116.1(C-3,,5,),161.8(C-4' ),104.1(C-1"), 76.0(C-2" ),78.4(C-3" ),71.3(C-4" ),76.0(C-5" ),64.2(C-6" ),125.5(C-1"'), 110.0(C-2" ' ),147.9(C-3" ' )149.4(C-4" ' ),115.4(C-5" ' ),123.4(C-6"'), 145.3(C-7"' ),114.5(C-8"' ),166.5(C-9"' ),55.7(-0CH3)
[0067] 实施例6取实施例2中粗黄酮50g,以硅胶干柱色谱法进行分离,洗脱剂为二氯甲 烷-丙酮(100 : 0-1 : 2),洗脱完成后将全柱分成8个组分,将各组分洗脱可得流份1-8。 将各流份用中低压快速色谱以ODS为填料进行梯度洗脱,流动相为甲醇-水(30 : 70、 50 : 50、80 : 20、100 : 0),其中50%甲醇洗脱、30%洗脱物进制备型HPLC制备,色谱条件 为乙腈:水:甲酸(15 : 85 : 0.04-40 : 60 : 0.04),可得化合物16-22。结构如下:
[0068]
[0071] 化合物16-22的碳氢谱数据如下:
[0072] 化合物16 :黄色粉末(甲醇)。盐酸-镁粉、MoIish反应为阳性。1H-Nmr^oomhz, DMS0-d6)SH:6.71(lH,br s,H-6),6.72(lH,br s,H-8),8.49(2H,d,J = 8.4Hz,H-2,, 6,),7.18(2H,d,J = 8.4Hz,H-3,,5,),6.14(lH,d,J = 7.8Hz,H-l" ),7.52(2H,d,J = 8·4Ηζ,Η-2",,6",),7.16(2H,d,J = 8.4Hz,H-3",,5",),7.84(lH,d,J=15.6Hz, H-7" ' ),6.49(lH,d,J=15.6Hz,H-8" ' ).13C-NMR(150MHz,DMS0-d6)Sc:157.8(C-2), 133. 4 (C-3),178. 8 (C-4),162. 7 (C-5),99. 9 (C-6),166. I (C-7),94. 7 (C-8),157. 6 (C-9), 105.2(010),121.8(01' ),131.9 (C-2',6' ),116.1 (C-3',5' ),161.8 (C-4'), 105.0(C-1" ),70.8(C-2" ),73.1(C-3" ),69.9(C-4" ),74.7(C-5" ),64.4(C-6"), 126.1(C-1" ' ),130.7(C-2" ',6" ' ),116.8(C-3" ',5" ' ),161.4(C-4"'), 145.3(C-7"' ),114.8(C-8"' ),167.2(C-9"'),
[0073] 化合物17 :黄色粉末(甲醇)。盐酸-镁粉、Mo I i sh反应为阳性。1H-NMR (400MHz, CD3OD) δ Η:6· 33(1H,d,J = 2. 3Hz,H-6),6· 12(1H,d,J = 2. 3Hz,H-8),8· 19(2H,d,J = 8.4Hz,H-2',6' ),7.20(2H,d,J = 8.4Hz,H-3',5' ),5.24(lH,d,J = 7.2Hz,H-l"), 7. 16(2H,s,H-2 " ',6 " ' ) · 13C-NMR(100MHz,CD3OD) δ c:158. I (C_2),135. 5 (C_3), 178. 3 (C-4),163. 9 (C-5),100. 2 (C-6),166. I (C-7),94. 2 (C-8),158. I (C-9),105. 2 (C-10), 121.8(01' ),131.9(C-2',6' ),116.1(C-3,,5,),161.8(C-4' ),100.1(C-1"), 76.1(C-2" ),76.0(C-3" ),69.8(C-4" ),77.2(C-5" ),61.1(C-6" ),122.8(C-1"'), 112.0(C-2" ',6" ' ),147.6(C-3" ',5" ' ),137.8(C-4" ' ),171.2(C-7" ' )·
[0074] 化合物is :黄色粉末(甲醇)。盐酸-镁粉、Moiisch反应为阳性。1H-Nmr^oomhz, DMS0-d 6) δ h:6. 19(1H,d,J = I. 8Hz,H-6),6. 40(1H,d,J = I. 8Hz,H-8),8. 49(2H,d,J = 8.4Hz,H-2',6' ),7.18(2H,d,J = 8.4Hz,H-3',5' ),5.36(lH,d,J = 7.8Hz,H-l"), 6.87(2H,s,H-2 " ',6 " ' ).13C-NMR(150MHz,DMS0-d6) Sc:156.3(C-2),133.5(C-3), 177. 4 (C-4),161. 2 (C-5),98. 7 (C-6),164. 2 (C-7),93. 6 (C-8),156. 4 (C-9),103. 9 (C-10), 121.8(01' ),131.9(C-2',6' ),116.1(C-3,,5,),161.8(C-4' ),100.1(C-1"), 71.1(C-2" ),72.8(C-3" ),67.8(C-4" ),72.4(C-5" ),62.0(C-6" ),119.1(C-1"'), 108.6(C-2" ',6" ' ),145.5(C-3" ',5" ' ),138.5(C-4" ' ),165.4(C = 0).
[0075] 化合物19 :黄色粉末(甲醇)。盐酸-镁粉、Moiisch反应为阳性。1H-Nmrgoomhz, DMSO-(I6) δ h:6. 23(1H,d,J = 2. 5Hz,h-6),6. 37(1H,d,J = 2. 5Hz,h-8),8. 52(2H,d,J = 8.3Hz,H-2',6' ),7.21(2H,d,J = 8.4Hz,H-3',5' ),5.44(lH,d,J = 7.5Hz,H-l"), 4.25(d,J= 12Hz,Ha-6" ),4.32(dd,J1=SHzJ2= 12Hz,Hb-6" ),6. 71 (2H,d,J = 8. 7Hz, H-2" ',H-6" ' ),7.56(2H,d,J = 8. 7Hz,H-3" ',H-5" ')· 13C-NMR(100MHz,DMS0-d6) δ c: 157. 2 (C-2),133. 5 (C-3),177. 9 (C-4, C = 0),161. 8 (C-5),99. 6 (C-6),165. 4 (C-7), 94. 6 (C-8), 157. 7 (C-9), 104. 5 (C-10), 121. 3 (C-Γ ),130. 9 (C-2r ,6r ),115. 6 (C-3r , 5 ' ),161.1(C-4 ' ),103.5(C-1 " ),72.4(C-2 " ),74.1(C-3 " ),69.5(C-4 "), 74.8(C-5" ),64.0(C
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