人参根以及根茎中新的聚乙炔类化学成份(三)

时间:2024-05-07 08:38:09来源:悬崖勒马网作者:时尚

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),根及根茎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]+,根及根茎份子式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,根及根茎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不同,故判断化合物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]+,份子式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不同,故判断化合物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]+,份子式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不同,故判断化合物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]+,份子式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)有短途相关,δ3.92(H-1)与186.0(C-3)有短途相关。以上数据与文献报道根基不同,故判断化合物9为东洋参炔醇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]+,份子式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不同,故判断化合物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]+,份子式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不同,故判断化合物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]+,份子式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不同,故判断化合物13为东洋参炔醇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]+,份子式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不同,故判断化合物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]+,份子式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不同,故判断化合物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]+,份子式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不同,故判断化合物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]+,份子式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不同,故判断化合物17为人参炔。

4品评辩说

人参中主要生物活性成份为三萜类化合物,搜罗原人参二醇型达玛烷皂苷、原人参三醇型达玛烷皂苷以及齐墩果烷型皂苷。本钻研从人参根以及根茎中患上到17个聚乙炔类化合物,搜罗2个新的化合物6以及10,以及3个初次从人参中分说患上到的聚乙炔类化合物四、9以及13,丰硕了人参化学成份的多样性,对于人参的公平开拓与利用具备确定的教育意思。本钻研患上到的聚乙炔类化合物绝大少数主链为17个碳,但化合物17为14个碳,比力特殊。最近,从人参中分说患上到对于乙酰胆碱酯酶具备抑制活性的高人参炔醇(homopanaxynol)以及高人参环氧炔醇(homopanaxydol);从野山参中又分说患上到1个新的聚炔类化合物,命名为人参炔氧苷A(panaxyneosideA);钻研了人参中某些聚炔类化合物妄想与过氧化物酶体增殖剂激活受体&ga妹妹a;(PPAR&ga妹妹a;)活化的构效关连。前期本课题组从传统中药白术中患上到妄想多样性的聚乙炔类化合物,对于脂多糖诱惑的巨噬细胞炎症反映具备精采的抑制作用,人参中这些聚乙炔类化合物的生物活性以及构效关连尚需深入钻研。

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相关链接:东洋参乙酰胆碱酯酶过氧化物酶

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