化合物5 白色粉末;ESI-MS m/z 353[M+Na]+; 1H-NMR(CD3OD,500 MHz)δ:7.10(1H,d,J=2.0 Hz,H-6),6.88(1H,dd,J=8.5,2.0 Hz,H-5),6.72(1H,d,J =2.0 Hz,H-2),4.80(1H,d,J=7.8 Hz,H-1′),3.85(1H,d,J=10.5,5.5 Hz,H-6′a),3.69(1H,d,J=10.5,2.4 Hz,H-6′b),3.65(2H,m,H-9),3.52(1H,m,H-2′),3.45(1H,m,H-3′),3.44(1H,m,H-5′),3.37(1H,m,H-4′),2.69(2H,m,H-7),1.93(2H,m,H-8); 13C-NMR(CD3OD,125 MHz)δ:150.5(C-3),146.0(C-4),131.7(C-1),124.8(C-6),118.6(C-5),116.6(C-2),103.6(C-1′),78.4(C-5′),77.8(C-3′),75.7(C-2′),71.5(C-4′),62.5(C-9),62.4(C-6′),36.4(C-7),35.9(C-8)。以上數據與文獻[14]報道基本一致,鑒定化合物5為3-羥基二氫肉桂醇-4-O-β-D-葡萄糖苷。
化合物6 淡黃色粉末;ESI-MS m/z 395[M+Na]+; 1H-NMR(CD3OD,500 MHz)δ:6.75(2H,s,H-2,6),6.55(1H,d,J=15.9 Hz,H-7),6.35(1H,dt,J=15.9,5.5 Hz,H-8),4.86(1H,d,J=7.6 Hz,H-1′),4.22(2H,dd,J=5.5,1.4 Hz,H-9),3.86(6H,s,3,5-OCH3),3.78(1H,d,J=10.9,5.2 Hz,H-6′a),3.66(1H,d,J=10.9,2.5 Hz,H-6′b),3.48(1H,m,H-2′),3.44(1H,m,H-3′),3.42(1H,m,H-5′),3.40(1H,m,H-4′); 13C-NMR(CD3OD,125 MHz)δ:154.4(C-3,5),135.3(C-1),135.2(C-4),131.3(C-7),130.1(C-8),105.4(C-2,6),102.6(C-1′),78.3(C-5′),77.8(C-3′),75.8(C-2′),71.4(C-4′),63.6(C-9),62.7(C-6′),57.0(3,5-OCH3)。以上數據和文獻[15]報道基本一致,確定化合物6為3,5-二甲氧基肉桂醇-4-O-β-D-葡萄糖苷。
化合物7 淡黃色粉末;ESI-MS m/z 395[M+Na]+; 1H-NMR(CD3OD,500 MHz)δ:7.10(1H,d,J=8.4 Hz,H-5),7.06(1H,d,J=2.0 Hz,H-2),6.95(1H,dd,J=8.4,2.0 Hz,H-6),6.56(1H,d,J=15.9 Hz,H-7),6.26(1H,dt,J=15.9,5.5 Hz,H-8),4.89(1H,d,J=7.6 Hz,H-1′),4.21(2H,dd,J=5.5,1.4 Hz,H-9),3.89(3H,s,3-OCH3),3.88(1H,d,J=10.6,5.3 Hz,H-6′a),3.69(1H,d,J=10.5,2.3 Hz,H-6′b),3.52(1H,m,H-2′),3.46(1H,m,H-3′),3.43(1H,m,H-5′),3.36(1H,m,H-4′); 13C-NMR(CD3OD,125 MHz)δ:151.0(C-3),147.7(C-4),131.3(C-7),129.0(C-8),127.3(C-1),120.8(C-6),116.2(C-5),111.5(C-2),102.8(C-1′),78.2(C-5′),77.9(C-3′),75.6(C-2′),71.4(C-4′),63.7(C-9),62.5(C-6′),56.8(3-OCH3)。以上數據和文獻[16]報道基本一致,確定化合物7為3-甲氧基肉桂醇-4-O-β-D-葡萄糖苷。
化合物8 淡黃色針晶(乙酸乙酯);mp 203~205 ℃; ESI-MS m/z 195[M+H]+; 1H-NMR(CD3OD,500 MHz)δ:7.90(1H,d,J=9.5 Hz,H-4),7.22(1H,s,H-5),6.78(1H,s,H-8),6.21(1H,d,J=9.5 Hz,H-3),3.83(3H,s,6-OCH3); 13C-NMR(CD3OD,125 MHz)δ:160.7(C-2),151.3(C-7),149.7(C-9),145.3(C-6),144.6(C-4),111.8(C-3),110.7(C-10),109.8(C-5),102.9(C-8),56.9(6-OCH3)。以上數據與文獻[17]報道基本一致,化合物8鑒定為東莨菪亭。
化合物9 淡黃色針晶(乙酸乙酯);mp 270~273 ℃; ESI-MS m/z 201[M+Na]+; 1H-NMR(DMSO-d6,500 MHz)δ:7.91(1H,d,J=9.5 Hz,H-4),7.16(1H,s,H-5),6.76(1H,s,H-8),6.22(1H,d,J=9.5 Hz,H-3); 13C-NMR(DMSO-d6,125 MHz)δ:170.1(C-2),150.7(C-7),148.8(C-9),144.7(C-4),143.0(C-6),112.8(C-5),111.9(C-3),111.3(C-10),103.1(C-8)。以上數據與文獻[18]報道基本一致,化合物9鑒定為6,7-二羥基香豆素。
化合物10 淡黃色粉末;HR-ESI-MS m/z 387.145 8[M+H]+(計算值387.144 4);1H-NMR(CDCl3,500 MHz)δ:7.59(1H,d,J=9.5 Hz,H-4),7.34(1H,d,J=8.6 Hz,H-5),6.80(1H,d,J=8.6 Hz,H-6),6.59(1H,J=4.5 Hz,H-9),6.23(1H,d,J=9.5 Hz,H-3),6.13(1H,dd,J=7.0,1.4 Hz,H-3′),5.41(1H,d,J=4.5 Hz,H-10),2.11(3H,s,4′-COCH3),1.95(1H,d,J=7.0 Hz,H-4′),1.87(1H,d,J=1.5 Hz,H-5′),1.48(3H,s,H-13),1.43(3H,s,H-12);13C-NMR(CDCl3,125 MHz)δ:169.8(4′-COCH3),166.5(C-1′),160.0(C-2),156.8(C-2′),154.0(C-8),143.3(C-4),139.7(C-3′),129.1(C-5),127.0(C-8a),114.3(C-6),113.2(C-3),112.5(C-7),107.1(C-4a),77.7(C-11),69.8(C-10),61.1(C-9),24.9(C-12),23.0(C-13),20.6(4′-COCH3),20.5(C-5′),15.5(C-4′)。以上數據與文獻[19]報道基本一致,化合物10鑒定為反式-3′-當歸酰基-4′-乙酰基角型吡喃香豆素。
化合物11 白色粉末;ESI-MS m/z 523[M+H]+;[α]25D+52.0(c 0.5,CH3OH); 1H,13C-NMR數據。數據與文獻[20]報道基本一致,化合物11鑒定為(+)-異落葉鬆脂素9′-O-β-D-葡萄糖苷。
化合物12 白色粉末;ESI-MS m/z 545[M+Na]+;[α]25D -30.8(c 0.8,CH3OH); 1H-NMR(CD3OD,500 MHz)δ:7.14(1H,d,J=8.5 Hz,H-5′),7.03(1H,d,J=1.9 Hz,H-2′),6.93(1H,dd,J=8.5,1.9 Hz,H-6′),6.73(1H,br s,H-2),6.72(1H,br s,H-6),5.55(1H,d,J=6.1 Hz,H-7′),4.88(1H,dd,J=7.5 Hz,H-1″),3.89(1H,dd,J=8.2,6.5 Hz,H-9′a,),3.87(3H,s,3-OCH3),3.84(1H,dd,J=12.2,5.5 Hz,H-6″a),3.81(3H,s,3′-OCH3),3.73(1H,dd,J=10.5,2.4 Hz,H-9′b),3.56(2H,t,J=6.5,H-9)3.45(1H,dd,J=12.4,6.0 Hz,H-6″b),2.86(1H,m,H-8′),3.30(1H,H-4″)3.26 m(1H,m,H-2″),3.28(1H,m,H-5″),2.62(2H,t,J=7.5,H-7),1.81(2H,m,H-8); 13C-NMR(CD3OD,125 MHz)δ:151.0(C-3′),147.6(C-4′),147.5(C-4),145.3(C-3),138.4(C-1′),137.1(C-1),129.6(C-5),119.4(C-6′),118.2(C-6),118.0(C-5′),114.3(C-4),111.3(C-2),102.9(C-1″),
88.5(C-7′),78.1(C-3″),77.9(C-2″),74.9(C-5″),71.4(C-4″),65.1(C-9′),62.5(C-6″),62.2(C-9),56.8(C-8′),56.8(3-OCH3),56.2(3′-OCH3),35.8(C-7),32.9(C-8)。以上數據與文獻[21]報道基本一致,化合物12鑒定為3,3′-二甲氧基-4,9,9′-三羥基-4′,7-環氧-5′,8-木脂素-4,9-O-β-D-二葡萄糖苷。