正文 鬼針草化學成分研究(2 / 3)

化合物6 黃色粉末;HR-ESI-TOF-MS m/z 311.052 2[M+Na]+(C15H12NaO6,計算值311.052 6); 1H-NMR(DMSO-d6,400 MHz)δ:7.17(1H,d,J=8.6 Hz,H-6′),6.94(1H,s,H-2′),6.80(1H,d,J=8.1 Hz,H-5′),6.75(1H,d,J=8.1 Hz,H-5),6.52(1H,d,J=8.6 Hz,H-6),5.38(1H,dd,J=11.8,2.8 Hz,H-2),3.03(1H,dd,J=16.7,2.8 Hz,H-3),2.68(1H,dd,J=16.7,2.8 Hz,H-3); 13C-NMR(DMSO-d6,100 MHz)δ:79.2(C-2),43.5(C-3),190.7(C-4),117.4(C-5),109.7(C-6),152.5(C-7),132.9(C-8),151.2(C-9),114.5(C-10),130.2(C-1′),114.4(C-2′),145.2(C-3′),145.6(C-4′),115.3(C-5′),118.0(C-6′)。以上數據與文獻[9]報道7,8,3′,4′-四羥基二氫黃酮的數據基本一致。

化合物7 白色粉末;HR-ESI-TOF-MS m/z 473.105 1[M+Na]+(C21H22NaO11,計算值473.105 4); 1H-NMR(DMSO-d6,400 MHz)δ:7.23(1H,d,J=8.8 Hz,H-5),6.92(1H,s,H-2′),6.86(1H,d,J=8.9 Hz,H-6),6.77(1H,s,H-6′),6.75(1H,s,H-5′),5.39(1H,dd,J=12.4,3.2 Hz,H-2),3.71(1H,d,J=8.0 Hz,H-6″a),3.48(1H,m,H-6″b),3.40~3.16(4H,H-2″~5″),3.11(1H,dd,J=16.7,2.8 Hz,H-3a),2.69(1H,dd,J=17.0,2.8 Hz,H-3b); 13C-NMR(DMSO-d6,100 MHz)δ:79.3(C-2),43.5(C-3),191.2(C-4),118.0(C-5),109.0(C-6),150.5(C-7),135.2(C-8),150.8(C-9),116.6(C-10),129.9(C-1′),114.5(C-2′),145.7(C-3′),145.2(C-4′),115.3(C-5′),116.4(C-6′),101.5(C-1″),73.2(C-2″),75.7(C-3″),69.7(C-4″),77.3(C-5″),60.7(C-6″)。核磁譜圖顯示為一組同分異構體,以上數據與文獻[10]中報道異奧卡寧-7-O-β-D-葡萄糖苷的數據基本一致,且異奧卡寧-7-O-β-D-葡萄糖苷僅有一個2位碳為手性中心,因此可確定該組化合物結構為異奧卡寧-7-O-β-D-葡萄糖苷(2R)(7a),異奧卡寧-7-O-β-D-葡萄糖(2S)(7b)。

化合物8 白色粉末;1H-NMR(CD3COCD3,300 MHz)δ:7.58(1H,d,J=8.8 Hz,H-5),7.28(1H,d,J=1.8 Hz,H-2′),7.1(1H,dd,J=8.1,1.9 Hz,H-6′),6.89(1H,d,J=4.4 Hz,H-5′),6.62(1H,d,J=8.7 Hz,H-6),5.55(1H,dd,J=12.9,2.9 Hz,H-2),4.78(1H,dd,J=7.3 Hz,H-1″),3.91(1H,d,J=3.0 Hz,H-OMe),3.58(1H,m,H-6″a),3.46(1H,m,H-6″b),3.34~3.14(4H,H-2″~ 5″),3.05(1H,m,H-3a),2.77(1H,m,H-3b); 13C-NMR(CD3COCD3,100 MHz)δ:81.1(C-2),44.7(C-3),190.7(C-4),124.6(C-5),111.1(C-6),156.5(C-7),134.0(C-8),157.9(C-9),115.8(C-10),131.5(C-1′),111.3(C-2′),147.8(C-3′),148.5(C-4′),116.1(C-5′),120.2(C-6′),107.0(C-1″),75.0(C-2″),77.4(C-3″),71.0(C-4″),78.1(C-5″),62.4(C-6″),56.5(3′-OCH3)。核磁譜圖顯示為一組同分異構體,以上數據數據與文獻[11]報道異奧卡寧-3′-甲氧基-7-O-β-D-葡萄糖苷的數據基本一致,且異奧卡寧-3′-甲氧基-7-O-β-D-葡萄糖苷隻有一個2位碳為手性中心,因此可確定此組化合物結構為異奧卡寧-3′-甲氧基-7-O-β-D-葡萄糖苷(2R)(8a),異奧卡寧-3′-甲氧基-7-O-β-D-葡萄糖苷(2R)(8b)。

化合物9 橘紅色粉末;HR-ESI-TOF-MS m/z 301.037 4[M-H]-(C15H9O7,計算值301.035 4);1H-NMR(DMSO-d6,400 MHz)δ:7.45(1H,s,H-2′),7.37(1H,d,J=8.2 Hz,H-6′),7.11(1H,d,J=8.1 Hz,H-4),6.85(1H,d,J=8.2 Hz,H-5′),6.73(1H,d,J=8.3 Hz,H-5),6.61(1H,s,H-10); 13C-NMR(DMSO-d6,100 MHz)δ:145.9(C-2),182.0(C-3),116.0(C-4),111.8(C-5),155.0(C-6),130.2(C-7),154.4(C-8),114.5(C-9),112.7(C-10),123.6(C-1′),118.4(C-2′),145.5(C-3′),148.0(C-4′),115.2(C-5′),124.6(C-6′)。以上數據與文獻[12]報道6,7,3′,4′-四羥基橙酮的數據基本一致。

化合物10 紅色粉末;1H-NMR(DMSO-d6,400 MHz)δ:7.46(1H,d,J=2.0 Hz,H-2′),7.34(1H,dd,J=8.3,1.9 Hz,H-6′),7.18(1H,d,J=8.5 Hz,H-4),7.07(1H,d,J=8.5 Hz,H-5),6.87(1H,d,J=8.3 Hz,H-5′),6.71(1H,s,H-10),4.94(1H,d,J=7.6 Hz,H-1″),3.72(1H,dd,J=10.7,4.3 Hz,H-6″a),3.49(1H,dt,J=11.8,5.9 Hz,H-6″b),3.40(1H,m,H-2″),3.40(1H,m,H-3″),3.32(1H,m,H-5″),3.21(1H,m,H-4″)。以上數據與文獻[10]報道海生菊苷的數據基本一致。

化合物11 黃色粉末;HR-ESI-TOF-MS m/z 201.015 4[M+Na]+(C9H6NaO4,計算值201.015 8); 1H-NMR(DMSO-d6,400 MHz)δ:7.84(1H,d,J=9.4 Hz,H-4),6.95(1H,s,H-5),6.68(1H,s,H-8),6.12(1H,d,J=9.4 Hz,H-3)。以上數據與文獻[13]報道6,7-二羥基香豆素的數據基本一致。

化合物12 白色粉末;1H-NMR(CD3COCD3,400 MHz)δ:7.63(1H,d,J=16.0 Hz,H-7),7.16(1H,d,J=1.9 Hz,H-2),7.04(1H,dd,J=8.2,1.9 Hz,H-6),6.87(1H,d,J=8.2 Hz,H-5),6.32(1H,d,J=16.0 Hz,H-8),5.34(1H,dd,J=4.2,0.8 Hz,H-3′),4.65(1H,dd,J=11.1,4.2 Hz,H-4a),4.32(1H,dd,J=11.1,0.8 Hz,H-4b),1.52(3H,s,5′-CH3); 13C-NMR(CD3COCD3,100 MHz)δ:127.4(C-1),116.4(C-2),146.3(C-3),149.0(C-4),115.2(C-5),122.8(C-6),146.9(C-7),114.8(C-8),177.5(C-1′),73.1(C-2′),75.4(C-3′),70.2(C-4′),22.4(C-5′),166.5(CO)。以上數據與文獻[14]報道3-咖啡酸酰基-2-甲基-D-赤蘚糖酸-1,4內酯的數據基本一致。

化合物 13 黃色粉末;[α]20D -16(c 0.05,MeOH); HR-ESI-TOF-MS m/z 541.167 7[M+Na]+(C26H30NaO11,計算值541.168 0); 1H-NMR(DMSO-d6,400 MHz)δ:9.60(1H,d,J=7.8 Hz, H-9′),7.65(1H,d,J=15.7 Hz,H-7′),7.32(1H,s,H-2′),7.31(1H,s,H-6′),7.11(1H,d,J=8.5 Hz,H-5),6.98(1H,d,J=1.8 Hz,H-2),6.86(1H,dd,J=8.5,1.8 Hz,H-6),6.72(1H,dd,J=15.7,7.8 Hz,H-8′),5.62(1H,d,J=6.0 Hz,H-7),4.89(1H,d,J=7.4 Hz,H-1″),3.85(3H,s,3′-OMe),3.85~3.76(2H,m,H-9),3.75(3H,s,3-OCH3),3.68(1H,m,H-6″a),3.52(1H,d,J=6.0 Hz,H-8),3.43(1H,m,H-6″b),3.30~3.17(4H,m,H-2″~5″); 13C-NMR(DMSO-d6,100 MHz)δ:134.7(C-1),110.5(C-2),149.0(C-3),146.4(C-4),115.4(C-5),118.20(C-6),87.8(C-7),52.7(C-8),62.7(C-9),127.9(C-1′),112.7(C-2′),144.2(C-3′),150.7(C-4′),130.0(C-5′),119.0(C-6′),154.0(C-7′),126.2(C-8′),194.1(C-9′),100.0(C-1″),73.2(C-2″),76.9(C-3″),69.7(C-4″),77.0(C-5″),60.7(C-6″),55.8(5-OCH3),55.9(5′-OCH3)。並利用1H-1H COSY,HSQC和HMBC進行碳氫信號歸屬。以上數據與文獻[15]報道(7S,8R)苯並二氫呋喃新木脂素-4-O-β-D-葡萄糖苷的數據基本一致。