正文 百尾參止咳活性成分研究(2 / 3)

化合物3 無色針狀晶體(石油醚-醋酸乙酯);mp 176~178 ℃;EI-MS m/z (%)238(M+·)(100),206,191,179,147,77,59;1H-NMR(DMSO-d6,400 MHz)δ: 9.55(1H,s,1′-NH),8.82(1H,s,1″-NH),7.46(1H,s,H-2),7.14(1H,d,J=8.0 Hz, H-6),7.04(1H,d,J=8.0 Hz,H-5),3.62(6H,s,2′,2″-OCH3),2.09(3H,s,4-CH3);13C-NMR(C5D5N,125 MHz)δ: 137.2(C-1),113.1(C-2),136.3(C-3),123.5(C-4),129.5(C-5),113.8(C-6),154.0(C-2′),153.5(C-2″),50.3(2′-OCH3),50.2(2″-OCH3),15.9(4-CH3)。以上光譜數據與文獻[14]報道的obtucarbamate A基本一致。

化合物4 無色針狀晶體(石油醚-醋酸乙酯);mp 172~174 ℃;EI-MS m/z (%)238(M+·),206,174,147(100),77,59;1H-NMR(DMSO-d6,400 MHz)δ: 8.92(2H,s,1′,1″-NH),7.10(3H,s,H-4~6),3.61(6H,s,2′,2″-OCH3),2.01(3H,s,2-CH3);13C-NMR(C5D5N,125 MHz)δ: 136.7(C-1,3),120.4(C-2),124.6(C-4,6),125.5(C-5),154.3(C-2′,2″),50.4(2′,2″-OCH3),11.7(2-CH3)。以上光譜數據與文獻[14]報道的obtucarbamate B基本一致。

化合物5 無色針狀晶體(石油醚-醋酸乙酯);mp 201~203 ℃;EI-MS m/z(%)416(M+·),344,302,287,273,139(100),115,69,41;1H-NMR(CDCl3,500 MHz)δ: 5.44(1H,br s,-OH),4.49(1H,m,H-16),3.94(1H,dd,J=10.8,2.8 Hz,H-26a),3.58(1H,br s,H-3),3.28(1H,dd,J=10.8,2.8 Hz,H-26b),1.09(3H,d,J=6.8 Hz,27-CH3),1.01(3H,d,J=6.8 Hz,21-CH3),0.83(3H,s,19-CH3),0.77(3H,s,18-CH3);13C-NMR(CD3COCD3,125 MHz)δ: 37.0(C-1),31.6(C-2),71.4(C-3),38.3(C-4),44.9(C-5),28.7(C-6),32.3(C-7),35.2(C-8),54.4(C-9),35.7(C-10),21.1(C-11),40.2(C-12),40.6(C-13),56.4(C-14),31.8(C-15),81.0(C-16),62.1(C-17),16.1(C-18),12.5(C-19),42.2(C-20),14.4(C-21),109.8(C-22),27.1(C-23),25.8(C-24),26.0(C-25),65.2(C-26),16.6(C-27)。以上碳譜數據與文獻[15]報道的neotigogenin基本一致,但該文獻中缺C-27的數據。因而結合文獻[16],鑒定該化合物為neotigogenin。

化合物6 淡黃色粉末;mp 307~309 ℃;EI-MS m/z (%)386(M+·),322,206,180,148(100),121,77;1H-NMR(C5D5N,500 MHz)δ: 9.78,9.24(各2H,s,-OH),8.38(2H,s,H-6′),7.64(2H,d,J=8.6 Hz,H-2),7.17(2H,d,J=8.6 Hz,H-1),3.66(3H,s,-OCH3),2.32(3H,s,-CH3);13C-NMR(C5D5N,125 MHz)δ: 130.9(C-1),115.8(C-2),137.9(C-1′),139.1(C-2′),153.8(C-3′),124.8(C-4′),155.5(C-5′),115.2(C-6′),51.8(-OCH3),17.5(-CH3)。以上數據與文獻[17]報道的偶氮-2,2′-雙 [Z-(2,3-二羥基- 4-甲基-5-甲氧基)苯基乙烯]基本一致。

化合物7 白色粉末;mp 230~232 ℃;EI-MS m/z(%)386(M+·),354,206,180(100),148,121,77,59;1H-NMR(DMSO-d6,400 MHz)δ: 8.81(2H,s,-NHCONH-),8.53(2H,s,-NHCOO-),7.52(2H,s,H-2,2′),7.14(2H,dd,J=8.4, 2.0 Hz,H-6,6′),7.06(2H,d,J=8.4 Hz,H-5,5′),3.64(6H,s,-OCH3),2.13(6H,s,7,7′-CH3);13C-NMR(C5D5N,125 MHz)δ: 137.0(C-1,1′),114.8(C-2,2′),138.3(C-3,3′),115.2(C-4,4′),130.8(C-5,5′),125.2(C-6,6′),17.6(CH3-7,7′),52.2(OCH3),155.3(-NHCONH-),153.0(-NHCOO-)。結合文獻[18]鑒定該化合物為dimethyl {[carbonylbis(azanediyl)]bis(2-methyl-5,1-phenylene)}dicarbamate,其波譜數據為首次報道。

化合物8 黃色粉末,Molish反應呈陽性,薄層色譜噴AlCl3後熒光增強;ESI-MS m/z 463.0 [M-H]-,487.1[M+Na]+;1H-NMR(DMSO-d6,500 MHz)δ: 12.62(1H,s,5-OH),7.56(1H,d,J=6.8 Hz,H-6′),7.54(1H,s,H-2′),6.8(1H,d,J=6.8 Hz,H-5′),6.38(1H,d,J=2.3 Hz,H-8),6.17(1H,d,J=2.3 Hz,H-6),5.44(1H,d,J=7.5 Hz,H-1″);13C-NMR(DMSO-d6,125 MHz)δ: 156.8(C-2),133.8(C-3),178.0(C-4),161.7(C-5),99.2(C-6),164.6(C-7),94.0(C-8),156.7(C-9),104.5(C-10),121.7(C-1′),115.7(C-2′),145.3(C-3′),149.0(C-4′),116.7(C-5′),122.1(C-6′),101.3(Glu-C-1),74.6(Glu-C-2),77.0(Glu-C-3),70.4(Glu-C-4),78.1(Glu-C-5),61.5(Glu-C-6)。以上波譜數據與文獻[19]報道的槲皮素-3-O-β-D-吡喃葡萄糖苷基本一致。