游客发表
化合物5:淡黄色油状物;[α]20D−52.9°(c0.12CHCl3);(cm−1):3423(brOH),人参2239(C≡C),根和根茎1584(C=C);(nm)(logε):200(3.43),中新226(3.13),乙炔257(3.02),类化276(3.22),学成291(3.26),人参303(3.33);ESI-MSm/z:301.1[M+Na]+,根和根茎分子式C17H26O3;1H-NMR(400MHz,中新CDCl3)δ:5.94(1H,乙炔ddd,类化J=17.1,学成10.0,人参5.3Hz,根和根茎H-2),中新5.46(1H,d,J=17.1Hz,H-1b),5.25(1H,d,J=10.0Hz,H-1a),4.92(1H,d,J=3.5Hz,H-3),3.65(1H,m,H-9),3.60(1H,m,H-10),2.59(2H,m,H-8),1.28~1.51(12H,m,H-11~16),0.88(3H,t,J=6.8Hz,H-17);13C-NMR(100MHz,CDCl3)δ:136.0(C-2),117.2(C-1),78.1(C-7),74.8(C-4),73.0(C-10),72.1(C-9),71.0(C-5),66.5(C-6),63.5(C-3),33.6(C-11),31.8(C-15),29.5(C-13),29.2(C-14),25.6(C-8),25.0(C-12),22.6(C-16),14.1(C-17)。以上数据与文献报道一致,故鉴定化合物5为(3R,9R,10R)-人参炔三醇。
化合物7:淡黄色油状物;[α]20D−98.2°(c1.20,CHCl3);(cm−1):3414(brOH),2236(C≡C),1641(C=C);(nm)(logε):206(3.33),229(3.00),241(2.88),256(2.68),272(2.48),287(2.40);ESI-MSm/z:281.1[M+Na]+,分子式C17H22O2;1H-NMR(400MHz,CDCl3)δ:5.89(1H,ddd,J=17.0,10.1,5.0Hz,H-2),5.80(1H,d,J=17.2,10.8,6.7Hz,H-16),5.45(1H,d,J=17.0Hz,H-1b),5.23(1H,d,J=10.1Hz,H-1a),4.98(1H,dd,J=17.2Hz,H-17b),4.93(1H,d,J=10.8Hz,H-17a),4.90(1H,d,J=5.0Hz,H-3),3.14(1H,ddd,J=7.2,5.4,4.2Hz,H-9),2.95(1H,td,J=5.9,4.2Hz,H-10),2.69(1H,dd,J=17.7,5.4Hz,H-8b),2.35(1H,dd,J=17.7,7.2Hz,H-8a),2.05(2H,q,J=6.2Hz,H-15),1.39~1.51(8H,m,H-11~14);13C-NMR(100MHz,CDCl3)δ:138.9(C-16),136.1(C-2),117.1(C-1),114.4(C-17),76.6(C-7),75.1(C-4),66.3(C-5),70.8(C-6),63.4(C-3),56.9(C-10),54.3(C-9),33.6(C-15),28.9(C-13),28.8(C-14),27.4(C-11),26.3(C-12),19.4(C-8)。以上数据与文献报道一致,故鉴定化合物7为人参炔A。
化合物8:淡黄色油状物;[α]20D−18.8°(c2.43,CHCl3);(cm−1):3418(brOH),2255(C≡C),1643(C=C);(nm)(logε):203(3.69),229(2.89),305(2.60);ESI-MSm/z:315.1[M+Na]+,分子式C18H28O3;1H-NMR(400MHz,CDCl3)δ:5.91(1H,ddd,J=17.0,10.2,5.4Hz,H-2),5.43(1H,d,J=17.0Hz,H-1b),5.20(1H,d,J=10.1Hz,H-1a),4.88(1H,d,J=4.9Hz,H-3),3.70(1H,dd,J=6.0,4.5Hz,H-10),3.41(3H,s,OCH3),3.22(1H,ddd,J=7.2,5.4,4.5Hz,H-9),2.55(1H,dd,J=17.4,6.5Hz,H-8a),2.53(1H,dd,J=17.4,6.2Hz,H-8b),1.23~1.52(12H,m,H-11~16),0.86(3H,t,J=6.9Hz,H-17);13C-NMR(100MHz,CDCl3)δ:136.2(C-2),116.9(C-1),82.1(C-9),78.3(C-7),74.7(C-5),70.9(C-4),70.9(C-10),66.1(C-6),63.3(C-3),58.4(OCH3),31.8(C-15),29.8(C-11),29.8(C-13),29.2(C-14),25.2(C-12),24.6(C-8),22.6(C-16),14.1(C-17)。以上数据与文献报道一致,故鉴定化合物8为10-甲氧基十七碳-1-烯-4,6-二炔-3,9-二醇。
化合物9:淡黄色油状物;[α]20D−106.15°(c0.09,CHCl3);(cm−1):3416(brOH),2237(C≡C),1642(C=C);(nm)(logε):204(4.36),230(3.31),240(3.32),254(3.52),269(3.74),284(3.73),305(3.38);ESI-MSm/z:299.1[M+Na]+,分子式C17H24O3;1H-NMR(400MHz,CDCl3)δ:3.92(2H,t,J=5.4Hz,H-1),3.17(1H,ddd,J=6.6,5.7,4.2Hz,H-9),2.98(1H,td,J=9.6,4.2Hz,H-10),2.85(2H,t,J=5.4Hz,H-2),2.76(1H,dd,J=18.0,5.7Hz,H-8b),2.49(1H,dd,J=18.0,6.6Hz,H-8a),2.04(1H,s,OH),1.52(1H,m,H-11),1.26~1.34(10H,m,H-12~16),0.88(3H,t,J=6.9Hz,H-17);13C-NMR(100MHz,CDCl3)δ:186.0(C-3),85.7(C-4),76.3(C-7),72.5(C-5),65.6(C-6),57.5(C-1),56.9(C-10),53.8(C-9),47.7(C-2),31.7(C-15),29.4(C-13),29.2(C-14),27.5(C-11),26.4(C-12),22.6(C-16),19.9(C-8),14.1(C-17)。在1H-1HCOSY谱中,δ3.92(H-1)与δ2.04(OH)以及δ2.85(H-2)相关,而在HMBC谱中,δ2.85(H-2)与δ57.5(C-1),186.0(C-3)有远程相关,δ3.92(H-1)与186.0(C-3)有远程相关。以上数据与文献报道基本一致,故鉴定化合物9为西洋参炔醇7。
化合物11:淡黄色油状物;[α]20D−20.9°(c1.22,CHCl3);(cm−1):3439(brOH),2237(C≡C),1646(C=C);(nm)(logε):202(3.68),230(3.18),241(3.04),257(3.02),274(3.09),289(3.04);ESI-MSm/z:299.1[M+K]+,分子式C17H24O2;1H-NMR(400MHz,CDCl3)δ:5.90(1H,ddd,J=17.0,10.1,5.4Hz,H-2),5.42(1H,d,J=17.0Hz,H-1b),5.20(1H,d,JJ=5.4Hz,H-3),3.11(1H,ddd,J=7.1,5.4,4.3Hz,H-9),2.95(1H,td,J=5.8,4.3Hz,H-10),2.68(1H,dd,J=17.7,5.4Hz,H-8b),2.35(1H,dd,J=17.7,7.1Hz,H-8a),1.26~1.50(12H,m,H-11~16),0.86(3H,t,J=7.0Hz,H-17);13C-NMR(100MHz,CDCl3)δ:136.0(C-2),116.8(C-1),76.4(C-7),75.1(C-4),70.5(C-5),66.3(C-6),63.2(C-3),57.0(C-10),54.3(C-9),31.6(C-15),29.3(C-13),29.0(C-14),27.3(C-11),26.3(C-12),22.5(C-16),19.3(C-8),14.0(C-17)。以上数据与文献报道一致,故鉴定化合物11为人参环氧炔醇。
化合物12:淡黄色油状物;[α]20D−56.3°(c4.05,CHCl3);(cm−1):3442(brOH),2236(C≡C),1646(C=C);(nm)(logε):202(3.33),227(2.95),241(2.82),256(2.77),273(2.77),289(2.74);ESI-MSm/z:285.1[M+Na]+,分子式C17H26O2;1H-NMR(400MHz,CDCl3)δ:4.35(1H,t,J=6.4Hz,H-3),3.13(1H,ddd,J=7.1,6.1,4.2Hz,H-9),2.96(1H,td,J=6.0,4.2Hz,H-10),2.69(1H,dd,J=17.7,6.1Hz,H-8b),2.37(1H,dd,J=17.7,7.1Hz,H-8a),1.73(2H,m,H-2),1.27~1.51(12H,m,H-11~16),1.00(3H,t,J=7.4Hz,H-1),0.88(3H,t,J=6.2Hz,H-17);13C-NMR(100MHz,CDCl3)δ:77.4(C-4),75.9(C-7),69.5(C-5),66.4(C-6),64.0(C-3),57.0(C-10),54.4(C-9),31.7(C-15),30.7(C-2),29.4(C-13),29.2(C-14),27.5(C-11),26.4(C-12),22.6(C-16),19.4(C-8),14.1(C-17),9.3(C-1)。以上数据与文献报道一致,故鉴定化合物12为人参炔D。
化合物13:淡黄色油状物;[α]20D−53.5°(c0.54,CHCl3);(cm−1):2236(C≡C),1673(C=C);(nm)(logε):203(4.00),231(3.18),244(3.03),258(3.24),272(3.46),288(3.43);ESI-MSm/z:297.1[M+Na]+,分子式C17H22O3;1H-NMR(400MHz,CDCl3)δ:3.54(1H,dd,J=3.9,2.2Hz,H-2),3.17(1H,ddd,J=6.6,5.7,4.1Hz,H-9),3.11(1H,dd,J=5.6,2.0Hz,H-1b),3.06(1H,dd,J=5.6,4.4Hz,H-1a),2.98(1H,td,J=6.0,4.1Hz,H-10),2.75(1H,dd,J=18.0,5.7Hz,H-8b),2.51(1H,dd,J=18.0,6.6Hz,H-8a),1.28~1.51(12H,m,H-11~16),0.87(3H,t,J=6.8Hz,H-17);13C-NMR(100MHz,CDCl3)δ:183.2(C-3),86.0(C-7),78.2(C-4),69.7(C-5),65.5(C-6),56.9(C-10),54.1(C-2),53.7(C-9),46.7(C-1),31.7(C-15),29.4(C-13),29.1(C-14),27.5(C-11),26.4(C-12),22.6(C-16),19.9(C-8),14.1(C-17)。以上数据与文献报道一致,故鉴定化合物13为西洋参炔醇4。
化合物14:淡黄色油状物;[α]20D−68.2°(c0.62,CHCl3);(cm−1):3450(brOH),2236(C≡C),1675(C=C);(nm)(logε):204(4.05),229(3.26),254(3.36),269(3.52),284(3.49),305(3.25);ESI-MSm/z:313.1[M+Na]+,分子式C18H26O3;1H-NMR(400MHz,CDCl3)δ:3.72(2H,t,J=6.1Hz,H-1),3.34(3H,s,OCH3),3.16(1H,ddd,J=6.7,5.7,4.9Hz,H-9),2.98(1H,td,J=9.1,4.9Hz,H-10),2.81(2H,t,J=6.1Hz,H-2),2.75(1H,dd,J=18.0,5.7Hz,H-8b),2.49(1H,dd,J=18.0,6.7Hz,H-8a),1.25~1.52(12H,m,H-11~16),0.88(3H,t,J=6.7Hz,H-17);13C-NMR(100MHz,CDCl3)δ:184.6(C-3),85.2(C-4),75.8(C-7),72.6(C-5),66.9(C-1),65.6(C-6),58.9(OCH3),56.9(C-10),53.8(C-9),45.5(C-2),31.7(C-15),29.4(C-13),29.1(C-14),27.5(C-11),26.4(C-12),22.6(C-16),19.9(C-8),14.1(C-17)。以上数据与文献报道一致,故鉴定化合物14为1-甲氧基-(9R,10S)-环氧十七碳-4,6-二炔-3-酮。
化合物15:淡黄色油状物;[α]20D−78.5(c0.92,CHCl3);(cm−1):3480(brOH),2237(C≡C),1716(C=O),1646(C=C);(nm)(logε):201(4.12),275(3.63),290(3.62);ESI-MSm/z:281.1[M+Na]+,分子式C17H22O2;1H-NMR(400MHz,CDCl3)δ:6.54(1H,d,J=17.4Hz,H-1b),6.40(1H,dd,J=17.4,10.2Hz,H-2),6.21(1H,d,J=10.2Hz,H-1a),3.16(1H,ddd,J=6.7,5.8,4.2Hz,H-9),2.98(1H,td,J=5.8,4.2Hz,H-10),2.76(1H,dd,J=18.0,5.8Hz,H-8b),2.50(1H,dd,J=18.0,6.7Hz,H-8a),1.45(2H,m,H-11),1.27~1.33(10H,m,H-12~16),0.87(3H,t,J=6.7Hz,H-17);13C-NMR(100MHz,CDCl3)δ:177.5(C-3),137.7(C-2),134.3(C-1),84.5(C-4),76.4(C-7),71.0(C-5),65.6(C-6),56.9(C-10),53.8(C-9),31.7(C-15),29.3(C-13),29.1(C-14),27.5(C-11),26.4(C-12),22.6(C-16),19.8(C-8),14.0(C-17)。以上数据与文献报道一致,故鉴定化合物15为人参炔E。
化合物16:淡黄色油状物;[α]20D−35.6°(c0.12,CHCl3);(cm−1):3411(brOH),2234(C≡C),1640(C=C);(2.82),254(3.39),268(3.66),284(3.59),306(2.72);ESI-MSm/z:283.1[M+Na]+,分子式C17H24O2;1H-NMR(400MHz,CDCl3)δ:6.32(1H,dd,J=15.9,5.6Hz,H-9),5.94(1H,ddd,J=17.0,10.1,4.7Hz,H-2),5.76(1H,d,J=15.9Hz,H-8),5.47(1H,d,J=17.0Hz,H-1b),5.25(1H,d,J=10.1Hz,H-1a),4.96(1H,d,J=4.7Hz,H-3),4.18(1H,dt,J=6.0,5.8Hz,H-10),1.52(2H,m,H-11),1.27~1.39(10H,m,H-12~16),0.87(3H,t,J=6.5Hz,H-17);13C-NMR(100MHz,CDCl3)δ:149.9(C-9),136.0(C-2),117.1(C-1),108.1(C-8),80.5(C-4),77.5(C-7),73.6(C-6),72.0(C-10),70.9(C-5),63.6(C-3),36.9(C-11),31.8(C-15),29.4(C-13),29.2(C-14),25.2(C-12),22.6(C-16),14.1(C-17)。以上数据与文献报道一致,故鉴定化合物16为人参炔二醇。
化合物17:淡黄色油状物;[α]20D−3.65°(c0.49,CHCl3);(cm−1):3363(brOH),2226(C≡C),1640(C=C);(nm)(logε):225(3.68),282(2.96),306(2.99);ESI-MSm/z:243.1[M+Na]+,分子式C14H20O2;1H-NMR(400MHz,CDCl3)δ:5.80(1H,ddd,J=17.2,10.2,7.6Hz,H-13),4.99(1H,d,J=17.2Hz,H-14a),4.93(1H,d,J=10.2Hz,H-14b),3.64(1H,s,H-6),3.59(1H,s,H-7),2.54(2H,brs,H-5),2.04(2H,m,H-12),2.00(1H,s,H-1),1.50(2H,m,H-8),1.36(6H,m,H-9~11);13C-NMR(100MHz,CDCl3)δ:139.0(C-13),114.3(C-14),74.5(C-4),73.0(C-7),72.1(C-6),68.1(C-2),66.8(C-3),65.3(C-1),33.7(C-12),33.5(C-8),29.0(C-10),28.8(C-11),25.4(C-9),24.7(C-5)。以上数据与文献报道一致,故鉴定化合物17为人参炔。
4讨论
人参中主要生物活性成分为三萜类化合物,包括原人参二醇型达玛烷皂苷、原人参三醇型达玛烷皂苷和齐墩果烷型皂苷。本研究从人参根和根茎中得到17个聚乙炔类化合物,包括2个新的化合物6和10,以及3个首次从人参中分离得到的聚乙炔类化合物4、9和13,丰富了人参化学成分的多样性,对于人参的合理开发与应用具有一定的指导意义。本研究得到的聚乙炔类化合物绝大多数主链为17个碳,但化合物17为14个碳,比较特殊。最近,从人参中分离得到对乙酰胆碱酯酶具有抑制活性的高人参炔醇(homopanaxynol)和高人参环氧炔醇(homopanaxydol);从野山参中又分离得到1个新的聚炔类化合物,命名为人参炔氧苷A(panaxyneosideA);研究了人参中某些聚炔类化合物结构与过氧化物酶体增殖剂激活受体γ(PPARγ)活化的构效关系。前期本课题组从传统中药白术中得到结构多样性的聚乙炔类化合物,对脂多糖诱导的巨噬细胞炎症反应具有良好的抑制作用,人参中这些聚乙炔类化合物的生物活性和构效关系尚需深入研究。
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相关链接:西洋参,乙酰胆碱酯酶,过氧化物酶
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