化合物4 白色無定形粉末;[α]29D-50.0°(c 0.100,MeOH);ESI-MS m/z 511 [M+Na]+。1H-NMR(DMSO-d6,500 MHz)δ:7.29(2H,d,J=8.5 Hz,H-2′,6′ ),7.01(2H,d,J=8.5 Hz,H-3′,5′),5.02(2H,s,H-7′),4.84(1H,d,J=7.5 Hz,H-1″),4.21(1H,br s,H-3),3.66(1H,br d,J=12.0 Hz,Hb-6″),3.48(3H,s,-OCH3),3.43(1H,dd,J=12.0,6.0 Hz,Ha-6″),3.32~3.12(4H,m,H-2″,3″,4″,5″),1.76(1H,dd,J=14.0,6.0 Hz,Hb-5),1.60(1H,m,H-6),1.55(1H,dd,J=14.0,6.0 Hz,Ha-5),0.85(3H,d,J=6.5Hz,H-8),0.71(3H,d,J=6.5 Hz,H-7);13C-NMR(DMSO-d6,125 MHz) δ:173.1(C-1),79.4(C-2),76.1(C-3),171.5(C-4),43.9(C-5),24.2(C-6),23.4(C-7),23.3(C-8),128.9(C-1′),129.9(C-2′),116.1(C-3′),157.3(C-4′),116.1(C-5′),129.9(C-6′),66.0(C-7′),100.3(C-1″),73.2(C-2″),76.6(C-3″),69.7(C-4″),77.0(C-5″),60.7(C-6″),51.5(-OCH3)。以上數據與文獻[33]報道基本一致,故鑒定該化合物為(-)-(2R,3S)-1-[4-(β-D-吡喃葡萄糖氧)苄基]-4-甲基-2-異丁基酒石酸酯。
化合物5 白色無定形粉末;[α]29D-38.5°(c 0.100,MeOH);ESI-MS m/z 799[M+Na]+。1H-NMR(DMSO-d6,500 MHz)δ:7.25(2H,d,J=8.5 Hz,H-2′,6′ ),7.22(2H,d,J=8.5 Hz,H-2,6 ),7.01(2H,d,J=8.5 Hz,H-3′,5′),7.00(2H,d,J=8.5 Hz,H-3,5 ),6.92(2H,d,J=8.5 Hz,H-7,11),6.61(2H,d,J=8.5 Hz,H-8,10 ),4.96(4H,s,H-7′,7),4.87(1H,d,J=8.0 Hz,H-1″),4.85(1H,d,J=8.0 Hz,H-1″″),3.69(2H,dt,J=11.5,5.5 Hz,Hb-6″,Hb-6″″),3.46(2H,td,J=11.5,5.5 Hz,Ha-6″,Ha-6″″),3.35~3.28 (2H,m,H-5″,5″″),3.28~3.20(4H,m,H-2″,3″,2″″,3″″),3.19~3.13(2H,m,H-4″,4″″),2.84(1H,d,J=16.0 Hz,Hb-3),2.83(1H,d,J=13.5 Hz,Hb-5),2.77(1H,d,J=13.5 Hz,Ha-5),2.48(1H,d,J=16.0 Hz,Ha-3)。13C-NMR(DMSO-d6,125 MHz)δ:173.7(C-1),75.6(C-2),42.6(C-3),169.7(C-4),43.8(C-5),125.7(C-6),131.5(C-7),114.7(C-8),156.2(C-9),114.7(C-10),131.5(C-11),129.3(C-1′),129.72(C-2′),116.21(C-3′),157.3(C-4′),116.21(C-5′),129.72(C-6′),65.9(C-7′),100.4(C-1″),73.3(C-2″),77.1(C-3″),69.8(C-4″),76.7(C-5″),60.8(C-6″),129.1(C-1),129.68(C-2),116.18(C-3),157.3(C-4),116.18(C-5),129.68(C-6),65.4(C-7),100.4(C-1″″),73.3(C-2″″),77.1(C-3″″),69.8(C-4″″),76.7(C-5″″),60.8(C-6″″)。以上數據與文獻[32]報道基本一致,故鑒定該化合物為vandaterosideⅡ。
化合物6 白色無定形粉末;[α]29D-49.2°(c 0.100,MeOH);ESI-MS m/z 783[M+Na]+。1H-NMR(DMSO-d6,500 MHz)δ:7.25(2H,d,J=8.5 Hz,H-2′,6′ ),7.21(2H,d,J=8.5Hz, H-2,6 ),7.19~7.21(3H,m,H-8,9,10),7.11(2H,dd,J=7.5 Hz,2.5 Hz,H-7,11),7.00(2H,d,J=8.5 Hz,H-3′,5′),6.99(2H,d,J=8.5 Hz,H-3,5 ),4.92~5.00(4H,m,H-7′,H-7),4.85(1H,d,J=7.5 Hz,H-1″),4.84(1H,d,J=7.5 Hz,H-1″″),3.67(2H,m,Hb-6″,Hb-6″″),3.47(2H,dd,J=12.0 Hz,6.0 Hz,Ha-6″,Ha-6″″),3.34~3.28(2H,m,H-5″,H-5″″),3.28~3.20(4H,m,H-2″,3″,H-2″″,3″″),3.18~3.12(2H,m,H-4″,H-4″″),2.94(1H,d,J=13.0 Hz,Hb-5),2.88(1H,d,J=13.0 Hz,Ha-5),2.87(1H,d,J=15.0 Hz,Hb-3),2.50(1H,d,J=15.0 Hz,Ha-3);13C-NMR(DMSO-d6,125 MHz)δ:173.4(C-1),75.3(C-2),42.6(C-3),169.5(C-4),44.3(C-5),135.6(C-6),130.4(C-7),127.8(C-8),126.5(C-9),127.8(C-10),130.4(C-11),129.1(C-1′),129.65(C-2′),116.1(C-3′),157.3(C-4′),116.1(C-5′),129.65(C-6′),65.9(C-7′),100.3(C-1″),73.2(C-2″),77.0(C-3″),69.7(C-4″),76.6(C-5″),60.67(C-6″),129.0(C-1),129.63(C-2),116.1(C-3),157.2(C-4),116.1(C-5),129.63(C-6),65.3(C-7),100.3(C-1″″),73.2(C-2″″),77.0(C-3″″),69.7(C-4″″),76.6(C-5″″),60.65(C-6″″)。以上數據與文獻[32]報道基本一致,故鑒定該化合物為grammatophylloside B。
化合物7 白色無定形粉末;[α]29D-44.6°(c 0.100,MeOH);ESI-MS m/z 735 [M+Na]+。1H-NMR(DMSO-d6,500 MHz)δ:7.28(2H,d,J=8.5 Hz,H-2′,6′ ),7.27(2H,d,J=8.5 Hz,H-2,6 ),7.01(4H,d,J=8.5 Hz,H-3′,5′,H-3,5 ),5.05(1H,d,J=12.0 Hz,Hb-7′),4.99(1H,d,J=12.0 Hz,Hb-7),4.97(1H,d,J=12.0 Hz,Ha-7′),4.95(1H,d,J=12.0 Hz,Ha-7),4.86(1H,d,J=7.5 Hz,H-1″),4.85(1H,d,J=7.5 Hz,H-1″″),3.68(2H,dd,J=11.5,3.0 Hz,Hb-6″,Hb-6″″),3.46(2H,dt,J=12.0,6.0 Hz,Ha-6″,Ha-6″″),3.35~3.20(6H,m,H-2″,3″,5″,H-2″″,3″″,5″″),3.16(2H,t,H-4″,H-4″″),2.84(1H,d,J=15.5 Hz,Hb-3),2.61(1H,d,J=15.5 Hz,Ha-3),1.83(1H,dd,J=13.5,7.0 Hz,H-5),0.82(3H,d,J=6.5 Hz,H-7),0.74(3H,d,J=6.5 Hz,H-6);13C-NMR(DMSO-d6,125 MHz) δ:174.1(C-1),77.4(C-2),41.9(C-3),170.2(C-4),35.7(C-5),16.3(C-6),17.2(C-7),129.3(C-1′),129.9(C-2′),116.3(C-3′),157.43(C-4′),116.3(C-5′),129.9(C-6′),66.0(C-7′),100.5(C-1″),73.4(C-2″),76.8(C-3″),69.9(C-4″),77.2(C-5″),60.8(C-6″),129.2(C-1),129.8(C-2),116.2(C-3),157.41(C-4),116.2(C-5),129.8(C-6),65.5(C-7),100.4(C-1″″),73.4(C-2″″),76.8(C-3″″),69.9(C-4″″),77.2(C-5″″),60.8(C-6″″)。以上數據與文獻[34]報道基本一致,故鑒定該化合物為(-)-(S)-1,4-二-[4-(β-D-吡喃葡萄糖氧)苄基]-2-異丙基蘋果酸酯。
化合物8 白色無定形粉末;[α]29D-38.4°(c 0.100,MeOH);ESI-MS m/z 481 [M+Na]+。1H-NMR(DMSO-d6,500 MHz)δ:7.28(2H,d,J=8.5 Hz,H-2′,6′ ),7.00(2H,d,J=8.5 Hz,H-3′,5′),5.02(1H,d,J=12.0 Hz,Hb-7′),5.00(1H,d,J=12.0 Hz,Ha-7′),4.84(1H,d,J=7.0 Hz,H-1″),3.67(1H,br d,J=12.0 Hz,Hb-6″),3.44(1H,dd,J=12.0,5.5 Hz,Ha-6″),3.32~3.12(4H,m,H-2″,3″,4″,5″),2.68(1H,d,J=16.0 Hz,Hb-3),2.42(1H,d,J=16.0 Hz,Ha-3),1.66(1H,m,Hb-5),1.54(1H,m,H-6),1.49(1H,m,Ha-5),0.85(3H,d,J=7.0 Hz,H-8),0.75(3H,d,J=7.0 Hz,H-7);13C-NMR(DMSO-d6,125 MHz) δ:174.7(C-1),75.0(C-2),45.3(C-3),173.9(C-4),47.7(C-5),23.5(C-6),23.5(C-7),24.4(C-8),129.3(C-1′),129.6(C-2′),116.1(C-3′),157.3(C-4′),116.1(C-5′),129.6(C-6′),65.7(C-7′),100.4(C-1″),73.3(C-2″),76.7(C-3″),69.8(C-4″),77.1(C-5″),60.8(C-6″)。以上數據與文獻[35]報道基本一致,故鑒定該化合物為gymnosideⅠ。
化合物9 白色無定形粉末;[α]29D-32.5°(c 0.100,MeOH);ESI-MS m/z 725 [M-H]-,761[M+Cl]-。1H-NMR(DMSO-d6,500 MHz) δ:7.26(4H,d,J=8.5 Hz,H-2′,6′,H-2,6),7.00(2H,d,J=8.5 Hz,H-3′,5′),6.99(2H,d,J=8.5 Hz,H-3,5),5.01(1H,d,J=11.0 Hz,Hb-7′),4.97(1H,d,J=11.0 Hz,Hb-7),4.95(1H,d,J=11.0 Hz,Ha-7′),4.93(1H,d,J=11.0 Hz,Ha-7),4.85(1H,d,J=7.5 Hz,H-1″),4.84(1H,d,J=7.5 Hz,H-1″″),3.67(2H,dd,J=10.5,4.5 Hz,Hb-6″,Hb-6″″),3.45(2H,m,Ha-6″,Ha-6″″),3.30(2H,m,H-3″,H-3″″),3.25(2H,m,H-5″,H-5″″),3.21(2H,m,H-2″,H-2″″),3.15(2H,m,H-4″,H-4″″),2.84(1H,d,J=15.0 Hz,Hb-3),2.57(1H,d,J=15.0 Hz,Ha-3),1.66(1H,m,Hb-5),1.55(1H,dd,J=12.0,6.0 Hz,H-6),1.53(1H,dd,J=12.0,6.0 Hz,Ha-5),0.83(3H,d,J=6.5 Hz,H-8),0.73(3H,d,J=6.5 Hz,H-7);13C-NMR(DMSO-d6,125 MHz) δ:174.2(C-1),75.0(C-2),44.9(C-3),169.7(C-4),47.7(C-5),23.4(C-6),23.4(C-7),24.4(C-8),129.3(C-1′),129.8(C-2′),116.2(C-3′),157.4(C-4′),116.2(C-5′),129.8(C-6′),66.0(C-7′),100.4(C-1″),73.3(C-2″),76.5(C-3″),69.8(C-4″),77.1(C-5″),60.8(C-6″),129.1(C-1),129.8(C-2),116.2(C-3),157.3(C-4),116.2(C-5),129.8(C-6),65.4(C-7),100.4(C-1″″),73.3(C-2″″),76.5(C-3″″),69.8(C-4″″),77.1(C-5″″),60.8(C-6″″)。以上數據與文獻[31]報道基本一致,故鑒定該化合物為militarine。