正文 華北藍盆花化學成分研究(2 / 3)

化合物6 黃色針狀結晶(甲醇),mp > 300 ℃。ESI-MS m/z 287 [M+H]+。1H-NMR(DMSO-d6,300 MHz)δ: 12.97(1H,s,5-OH),7.42(1H,br d,J=7.2 Hz,H-6′),7.39(1H,br s,H-2′),6.87(1H,d,J=7.2 Hz,H-5′),6.66(1H,s,H-3),6.43(1H,d,J=1.8 Hz,H-8),6.17(1H,d,J=1.8 Hz,H-6)。13C-NMR(DMSO-d6,75 MHz) δ:163.9(C-2),102.9(C-3),181.7(C-4),157.3(C-5),98.9(C-6),164.2(C-7),93.9(C-8),161.5(C-9),103.7(C-10),121.5(C-l′),113.3(C-2′),145.8(C-3′),149.7(C-4′),116.0(C-5′),119.0(C-6′)。以上數據與文獻[11]報道基本一致,故鑒定其結構為木犀草素(luteolin)。

化合物7 白色粉末(甲醇),mp 258~260 ℃。ESI-MS m/z 577[M+H]+。1H-NMR(pyridine-d5,300 MHz) δ: 0.93,0.90,0.88,0.87,0.86,0.66(6×CH3), 5.34(1H,m,H-6),5.00(1H,d,J=6.9 Hz,H-1′)。13C-NMR(pyridine-d5,75 MHz)δ: 37.5(C-1),30.3(C-2),78.1(C-3),39.4(C-4),140.9(C-5),121.9(C-6),32.2(C-7),32.1(C-8),50.4(C-9),36.4(C-10),21.3(C-11),40.0(C-12),42.5(C-13),56.8(C-14),24.5(C-15),28.6(C-16),56.3(C-17),12.0(C-18),19.2(C-19),36.9(C-20),19.0(C-21),34.2(C-22),26.4(C-23),46.1(C-24),29.5(C-25),19.4(C-26),20.0(C-27),23.4(C-28),12.2(C-29),102.6(C-1′),75.4(C-2′),78.6(C-3′),71.8(C-4′),78.5(C-5′),62.9(C-6′)。以上數據與文獻[12]報道基本一致,故鑒定其結構為胡蘿卜苷(daucosterol)。

化合物8 黃色粉末(甲醇),mp 214~215 ℃。ESI-MS m/z 617 [M+Na]+。1H-NMR(DMSO-d6,300 MHz) δ: 6.14(1H,d,J=2.0 Hz,H-6),6.37(1H,d,J=2.0 Hz,H-8),7.98(2H,d,J=8.8 Hz,H-2′,6′),6.84(2H,d,J=8.8 Hz,H-3′,5′),5.57(1H,d,J=7.8 Hz,H-1″),6.77(2H,d,J=8.4 Hz,H-2,H-6),7.36(2H,d,J=8.4 Hz,H-3,H-5),7.33(1H,d,J=16.0 Hz,H-7),6.10(1H,d,J=16.0 Hz,H-8)。13C-NMR(DMSO-d6,75 MHz)δ:156.3(C-2),133.0(C-3),177.4(C-4),161.1(C-5),98.7(C-6),164.2(C-7),93.6(C-8),156.4(C-9),103.8(C-10),120.7(C-l′),130.8(C-2′,6′),115.1(C-3′,5′),160.0(C-4′),100.9(C-1″),74.2(C-2″),76.2(C-3″),69.9(C-4″),74.1(C-5″),62.9(C-6″),124.9(C-1),130.1(C-2,6),115.7(C-3,5),159.8(C-4),144.6(C-7),113.6(C-8),166.1(C-9)。以上數據與文獻[13]報道基本一致,故鑒定其結構為山柰酚-3-O-β-D-[6-O-(對羥基桂皮酰基)-吡喃葡萄糖苷[kaempferol-3-O-β-D-6-O-(p-hydroxycinnamoyl)-glucopyranoside]。

化合物9 黃色粉末(甲醇),mp 229~230 ℃。ESI-MS m/z 763 [M+Na]+。1H-NMR(DMSO-d6,300 MHz)δ: 6.17(1H,d,J=2.1 Hz,H-6),6.39(1H,d,J=2.0 Hz,H-8),7.99(2H,d,J=8.7 Hz,H-2′,6′),6.87(2H,d,J=9.0 Hz,H-3′,5′),5.58(1H,d,J=7.8 Hz,H-1″),7.52(2H,d,J=8.4 Hz,H-2,H-6),6.79(2H,d,J=8.4 Hz,H-3,H-5),6.42(1H,d,J=16.0 Hz,H-7),7.59(1H,d,J=16.0 Hz,H-8),7.39(2H,d,J=8.7 Hz,H-2″″,H-6″″),6.87(2H,d,J=9.0 Hz,H-3″″,H-5″″),6.15(1H,d,J=15.9 Hz,H-7″″),7.37(1H,d,J=15.9 Hz,H-8″″)。13C-NMR(DMSO-d6,75 MHz)δ:156.4(C-2),133.0(C-3),177.3(C-4),161.2(C-5),98.8(C-6),164.3(C-7),93.7(C-8),156.6(C-9),103.9(C-10),120.7(C-l′),130.9(C-2′,6′),115.2(C-3′,5′),160.1(C-4′),100.9(C-1″),72.1(C-2″),76.8(C-3″),68.0(C-4″),74.0(C-5″),62.7(C-6″),125.2(C-1),130.2(C-2,6),115.8(C-3,5),159.8(C-4),144.7(C-7),113.6(C-8),166.1(C-9),124.9(C-1″″),130.2(C-2″″,6″″),115.8(C-3″″,5″″),159.8(C-4″″),144.7(C-7″″),114.7(C-8″″),166.2(C-9″″)。以上數據與文獻[14]報道基本一致,故鑒定其結構為山柰酚-3-O-β-D-[3,6-二-(對羥基桂皮酰)]-吡喃葡萄糖苷[kaempferol-3-O-β-D-(3,6-di-p-hydroxycinnamoyl)-glucopyranoside]。

化合物10 黃色無定形粉末(甲醇),mp 227~229 ℃。ESI-MS m/z 455 [M+Na]+。1H-NMR(DMSO-d6,300 MHz)δ:12.97(1H,s,5-OH),7.94(2H,d,J=8.4 Hz,H-2′,H-6′),6.91(2H,d,J=8.4 Hz,H-3′,H-5′),6.85(1H,s,H-3),6.82(1H,d,J=1.8 Hz,H-8),6.43(1H,d,J=1.8 Hz,H-6),5.06(1H,d,J=7.2 Hz,H-1″),3.69(1H,d,J=8.4 Hz,H-6″)。13C-NMR(DMSO-d6,75 MHz)δ:164.3(C-2),102.9(C-3),182.0(C-4),156.9(C-5),99.5(C-6),163.0(C-7),94.8(C-8),161.8(C-9),105.3(C-10),120.7(C-1′),128.6(C-2′,C-6′),116.0(C-3′,5′),161.1(C-4′),99.9(C-1″),73.1(C-2″),76.4(C-3″),69.5(C-4″),77.2(C-5″),60.6(C-6″)。以上數據與文獻[15]報道基本一致,故鑒定其結構為芹菜素-7-O-β-D-吡喃葡萄糖苷(apigenin-7-O-β-D-glucopyranoside)。

化合物11 黃色塊狀結晶(甲醇,乙醇),mp 188~192 ℃。ESI-MS m/z 449 [M+H]+。1H-NMR(DMSO-d6,300 MHz)δ:12.91(1H,s,5-OH),10.87(1H,s,7-OH),7.52(1H,br d,J=8.4 Hz,H-6′),7.49(1H,br s,H-2′),7.22(1H,d,J=8.4 Hz,H-5′),6.82(1H,s,H-3),6.49(1H,s,H-8),6.19(1H,s,H-6),4.88(1H,d,J=6.3 Hz,H-1″)。13C-NMR(DMSO-d6,75 MHz) δ:163.2(C-2),103.8(C-3),181.8(C-4),161.4(C-5),98.9(C-6),161.4(C-7),94.0(C-8),157.3(C-9),104.0(C-10),124.6(C-1′),113.6(C-2′),146.9(C-3′),148.5(C-4′),116.0(C-5′),118.5(C-6′),101.2(C-1″),73.2(C-2″),75.8(C-3″),77.3(C-4″),69.8(C-5″),60.7(C-6″)。以上數據與文獻[16]報道基本一致,故鑒定其結構為木犀草素-4′-O-β-D-吡喃葡萄糖苷(luteolin-4′-O-β-D-glucopyranoside)。

化合物12 淡黃色粉末(甲醇),mp 272~274 ℃。ESI-MS m/z 579 [M+H]+。1H-NMR(DMSO-d6,300 MHz)δ:12.95(1H,s,5-OH),10.37(1H,s,4′-OH),7.94(2H,d,J=8.7 Hz,H-2′,6′),6.94(2H,d,J=8.7 Hz,H-3′,5′),6.86(1H,s,H-3),6.77(1H,s,H-8),6.44(1H,s,H-6),5.06(1H,d,J=7.5 Hz,H-1″),4.60(1H,br s,H-1),1.07(3H,d,J=6.3 Hz,H-6)。13C-NMR(DMSO-d6,75 MHz) δ:164.4(C-2),103.1(C-3),182.0(C-4),162.9(C-5),99.5(C-6),161.3(C-7),94.8(C-8),156.9(C-9),105.4(C-10),121.0(C-1′),128.7(C-2′,6′),116.1(C-3′,5′),161.2(C-4′),100.5(C-1″),72.1(C-2″),75.6(C-3″),70.7(C-4″),76.3(C-5″),66.0(C-6″),99.9(C-1),69.5(C-2),70.3(C-3),73.1(C-4),68.3(C-5),17.8(C-6)。以上數據與文獻[17]報道基本一致,故鑒定其結構為芹菜素-7-O-蘆丁糖苷(apigenin-7-O-rutinoside)。

化合物13 黃色粉末(甲醇),mp>300 ℃。ESI-MS m/z 449 [M+H]+。1H-NMR(DMSO-d6,400 MHz) δ: 12.88(1H,s,5-OH),7.51(1H,br d,J=8.2 Hz,H-6′),7.48(1H,br s,H-2′),7.22(1H,d,J=8.2 Hz,H-5′),6.80(1H,s,H-3),6.46(1H,d,J=1.8 Hz,H-8),6.17(1H,d,J=1.8 Hz,H-6)。13C-NMR(DMSO-d6,100 MHz) δ:164.5(C-2),103.6(C-3),181.6(C-4),161.4(C-5),98.9(C-6),163.1(C-7),93.9(C-8),157.3(C-9),103.9(C-10),121.5(C-l′),113.3(C-2′),145.8(C-3′),149.7(C-4′),116.0(C-5′),119.0(C-6′),101.2(C-1″),73.1(C-2″),75.8(C-3″),69.7(C-4″),77.2(C-5″),60.6(C-6″)。以上數據與文獻[18]報道基本一致,故鑒定其結構為木犀草素-7-O-β-D-葡萄吡喃糖苷(luteolin-7-O-β-D-glucopyranoside)。

化合物14 黃色粉末(甲醇),mp 340.0~341.0 ℃。ESI-MS m/z 455 [M+Na]+。1H-NMR(DMSO-d6,400 MHz) δ:7.84(2H,d,J=8.8 Hz,H-2′,6′),6.88(2H,d,J=8.8 Hz,H-3′,5′),6.60(1H,s,H-3),6.76(1H,d,J=2.0 Hz,H-8),6.44(1H,d,J=2.0 Hz,H-6),5.05(1H,d,J=7.0 Hz,H-1″),3.89(1H,dd,J=10.0 Hz,6.0 Hz,H-6b″),3.86(1H,dd,J=10.0,2.0 Hz,H-6a″),3.20 ~ 3.50(4H,m,H-2″,3″,4″,5″)。13C-NMR(DMSO-d6,100 MHz) δ:166.8(C-2),104.1(C-3),184.1(C-4),162.9(C-5),101.6(C-6),164.8(C-7),96.0(C-8),158.1(C-9),104.1(C-10),123.1(C-1′),129.6(C-2′,6′),117.0(C-3′,5′),159.0(C-4′)。以上數據與文獻[19]報道基本一致,故鑒定其結構為芹菜素-4′-O-β-D-吡喃葡萄糖苷(apigenin-4′-O-β-D-glucopyranoside)。

化合物15 淺黃色粉末(甲醇),mp 152~153 ℃。ESI-MS m/z 193[M-H]-。1H-NMR(CD3OD,300 MHz) δ:7.02(1H,d,J=1.8 Hz,H-2),6.92(1H,dd,J=1.8,8.4 Hz,H-6),6.76(1H,d,J=8.4 Hz,H-5),7.53(1H,d,J=15.9 Hz,H-7),6.24(1H,d,J=15.9 Hz,H-8),3.74(3H,s,-OCH3)。13C-NMR(CD3OD,75 MHz) δ:127.7(C-1),116.5(C-2),146.9(C-3),149.6(C-4),122.9(C-5),115.1(C-6),146.8(C-7),114.8(C-8),169.8(C-9),52.0(-OCH3)。以上數據與文獻[20]報道基本一致,故鑒定其結構為咖啡酸甲酯(caffeic acid methylester)。

化合物16 白色粉末(甲醇),mp 221~222 ℃。ESI-MS m/z 389[M-H]-。1H-NMR(DMSO-d6,300 MHz)δ:5.11(1H,d,J=4.8 Hz,H-1),7.35(1H,s,H-3),3.13(1H,m,H-5),1.70(1H,m,H-6α),4.46(1H,m,H-7),1.83(1H,m,H-8),2.05(1H,m,H-9),0.97(3H,d,J=6.9 Hz,H-10),3.61(3H,s,OCH3),5.01(1H,d,J=5.4 Hz,H-1′),3.43(1H,m,H-3′),3.87(1H,m,H-6′)。13C-NMR(DMSO-d6,75 MHz) δ:96.1(C-1),150.6(C-3),112.1(C-4),30.8(C-5),41.7(C-6),73.1(C-7),44.7(C-8),40.5(C-9),13.5(C-10),167.0(C-11),50.9(OCH3),98.6(C-1′),72.1(C-2′),77.3(C-3′),70.1(C-4′),76.8(C-5′),61.2(C-6′)。以上數據與文獻[21]報道基本一致,故鑒定其結構為馬錢素(loganin)。