七里香的化学成分研究

崔小燕，刘亚平，衣 振，程桂广

(1.昆明医科大学海源学院, 云南 昆明 650106；2.昆明理工大学 农业与食品学院，云南 昆明 650500;3.山东职健检测技术有限公司，山东 聊城 252000)

醉鱼草属(Buddleja)是马钱科中最大的属，多为灌木，少有乔木和亚灌木状草本，分布于美洲、非洲和亚洲的热带至温带地区，我国醉鱼草属植物资源丰富，约有29个种.该属植物许多种具有观赏和药用价值，具有较强的生物活性，在世界很多地区作为传统用药.七里香(BuddlejaasiaticaLour)，为马钱科醉鱼草属植物，直立灌木或亚灌木，生于海拔200～3 000 m 的向阳山坡灌木丛中或疏林缘.全草药用，有驱风化湿、行气活络之功效，用于治疗发烧、疼痛、痢疾和关节炎[1].

对醉鱼草属植物的化学成分研究较多，报道的结构类型多为三萜及其苷[2-3]、黄酮及其苷[4]、环烯醚萜苷[5]、倍半萜烯[6]、二萜[7]及皂苷[8].但对七里香(B.asiatica)化学成分的报道较少，对其甲醇提取物乙酸乙酯萃取部分进行分离，得16个化合物，通过核磁共振、质谱及相应文献鉴定结构：(-)-diasesamin-di-γ-lactone (1)[9],(-)-aptosimon(2)[10],(+)-sesamin (3)[11],luteolin(4)[12],5,7-dihydroxyflavone(5)[13],3,4′,5-trihydroxy-7-methoxyflavone(6)[14], 5,7-dihydroxychromone (7)[15],maslinic acid (8)[16],β-amyrin(9)[17],oleanolic aldehyde (10)[18],oleanolic acid (11)[18],11-hydroxy-8(14),15-isopimaradien-7-one (12)[19], jioglutolide (13)[20], ningpogenin (14)[21], 3β-Hydroxy-5α,8α-epidioxyergosta-6,11,22-diene (15)[11],3β-Hydroxy-5α,8α-epidioxyergosta-6,22-diene (16)[22](图1).

1 实验部分

1.1 材料与仪器

Bruker DRX - 500核磁共振波谱仪(德国Bruker公司)；VG Autospec-3000电子轰击质谱；EYELA OSB-2100旋转蒸发仪(上海爱朗仪器有限公司)；中压分离装置(瑞士步琦有限公司)；薄层层析硅胶板(青岛谱科有限公司)；葡聚糖凝胶Sephadex LH-20(Pharmacia化学公司)；RP-C18gel (Merck公司)；色谱甲醇、乙腈(Merck公司)；化合物先在荧光灯UV (254、365 nm)下观察，后喷洒含有茴香醛的硫酸乙醇溶液，最后 100 ℃ 加热5～10 min.

图1 七里香中化合物1～16结构图

七里香(B.asiatica)采自中国广西，由曾春霞博士鉴定，标本存放在中科院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室.

1.2 提取与分离

七里香(B.asiatica)样品(8.5 kg)晒干粉碎，甲醇室温浸提4 d，减压浓缩乙酯萃取4次，得浸膏(130 g)，经硅胶柱层析(CHCl3-Me2CO 1∶0～1∶1)，TLC检测合并得6个组分(Ⅰ～Ⅵ).组分Ⅱ(54 g)经硅胶柱层析(体积比，石油醚∶丙酮=30∶1～10∶1)得Ⅱ-1～Ⅱ-5.Ⅱ-2(8 g)经硅胶柱分离(体积比，石油醚∶乙酸乙酯=10∶1～2∶1)得到12(5 mg)和1(6 mg).Ⅱ-3(10 g)经RP-18反相柱层析(体积分数,甲醇∶水=60%～90%)，再经凝胶柱层析(体积比，甲醇∶氯仿=1∶1)得2(126 mg)，3(2 mg) 和8(43 mg).组分Ⅲ(20 g)经RP-18反相柱层析(体积分数，甲醇∶水=60%～90%)得Ⅲ-1～Ⅲ-4.Ⅲ-4(1 g)经硅胶柱(体积比，石油醚∶乙酯=12∶1,7∶1，5∶1)洗脱得9(40 mg)和10(23 mg).Ⅲ-3(5 g)经硅胶柱(体积比，石油醚∶乙酯=12∶1～1∶1)纯化得15(20 mg)和16(76 mg).组分Ⅳ(21 g)经RP-18反相柱层析(体积分数，甲醇∶水=40%～80%)，再经硅胶柱(体积比，石油醚∶乙酯=12∶1～1∶1)洗脱得11(52 mg)，7(14 mg) 和5(15 mg).组分Ⅴ(20 g)经过RP-18反相柱层析(体积分数，甲醇∶水=30%～70%)，再经凝胶柱层析(甲醇)得4(9 mg)和6(198 mg).组分Ⅵ(3 g)经硅胶柱层析(体积比,氯仿∶甲醇=10∶1～2∶1)，再经中压柱层析(体积分数，甲醇∶水=30%～60%)，再经凝胶柱纯化(甲醇)得13(90 mg)和14(36 mg).

2 结构鉴定

化合物1黄色晶体，C20H14O8.EIMS (m/z):382 [M]+.1H NMR(400 MHz,CDCl3)δH:3.55(2H,br.s,H-1,1′),5.83(2H,br.s,H-2,2′),5.99(4H,-OCH2O-× 2);6.76(2H,s,H-2′,2″);13C NMR (CDCl3,100 MHz)δC:131.7(s,C-1′,1″),105.2(d,C-2′,2″),148.3(s,C-3′,3″),148.5(s,C-4′,4″),108.7(d,C-5′,5″),118.5 (d, C-6′,6″), 48.3 (d, C-1, 5), 81.2(d,C-2,6),174.6(s,C-4,8),101.6(t,-OCH2O-×2).以上数据与文献[9]报道基本一致，故鉴定1的结构为(-)-diasesamin-di-γ-lactone.

化合物2白色晶体，C20H16O7.EIMS(m/z)：368[M]+.1H NMR (400 MHz,CDCl3)δH:6.85(2H,d,J=1.2 Hz,H-2′,2″),5.96(2H,-OCH2O-×2),5.93(2H,-OCH2O-×2);5.28(2H,br.s,H-2,6),4.32(1H,dd,J=7.0,9.4 Hz,H-8a),4.00(1H,dd,J=4.7,9.4 Hz,H-8b),3.42(1H,m,H-5),3.20(1H,br.s,H-1);13C NMR (CDCl3, 100 MHz)δC:134.3(s,C-1′),108.5(d,C-2′),148.4(s,C-3′),148.0(s,C-4′),105.9(d,C-5′),119.0(d,C-6′),133.0(s,C-1″),108.3(d,C-2″),148.0(s,C-3″),147.3(s,C-4″),105.7(d,C-5″),118.7(d,C-6″),49.8(d,C-1),83.4(d,C-2),176.6(s,C-4),53.2(d,C-5),84.4(d,C-6),72.6(t,C-8),101.1(s,-OCH2O-),101.4(s,-OCH2O-).以上数据与文献[10]报道基本一致，故鉴定2的结构为(-)-aptosimon.

化合物3白色针状晶体，C20H18O6.EIMS(m/z)：354 [M]+.1H NMR (400 MHz, CDCl3)δH:6.85(2H,s,H-2′,2″),5.96(4H,-OCH2O-×2);4.72(2H,d,J=4.3 Hz,H-2,6),3.06(2H,br.s,H-1,5);13C NMR(CDCl3,100 MHz)δC:135(s,C-1′,1″),106.5(d,C-2′,2″),147.9(s, C-3′,3″),147.1(s,C-4′,4″),108.2(d,C-5′,5″),119.3(d,C-6′,6″),55.3(d,C-1,5),87.5(d,C-2,6),71.7(d,C-4.8),101.5(s,-OCH2O-× 2).以上数据与文献[11]报道基本一致，故鉴定3的结构为 (+)-sesamin.

化合物4黄色晶体，C15H10O6.1H NMR (DMSO, 400 MHz)δH:7.94(1H,s,H-2′),7.92(1H,d,J=8.8 Hz,H-6′),7.44(1H,d,J=8.8 Hz,H-5′),6.96(1H,s,H-3),6.79(1H,s,H-3),7.00(1H,d,J=2.0 Hz,H-8),6.69(1H,d,J=2.0 Hz,H-6).13C NMR(DMSO,100 MHz)δC:181.9(s,C-4),164.5(s,C-2),164.7(s,C-7),162.1(s,C-5),157.9(s,C-8a),150.1(s,C-4′),146.2(s,C-3′),122.1(s,C-1′),113.8(d,C-2′),116.4(d,C-5′),119.3(d,C-6′),104.2(s, C-4a),103.3(s,C-3),99.2(d,C-6),94.2(d,C-8).以上数据与文献[12]报道基本一致，故鉴定4的结构为luteolin.

化合物5黄色晶体，C15H10O4.1H NMR(CD3COCD3,500 MHz)δH:8.51(2H,d,J=7.1Hz,H-2′,6′),6.79(1H,s,H-3),7.24(1H,s,H-8),7.02(1H,s,H-6),6.72(1H,s,H-3).13C NMR(CD3COCD3,125 MHz)δC:163.1(s,C-2),105.1(d,C-3),181.6(s,C-4),161.5(s,C-5),94.0(d,C-6),164.6(s,C-7),94.1(d,C-8),157.5(s,C-9),103.9(s,C10),130.7(s,C-1′),129.0(d,C-2′,6′),126.3(d,C-3′,5′),131.9(d,C-4′).以上数据与文献[13]报道基本一致，故鉴定5的结构为 5,7-dihydroxyflavone.

化合物6黄色晶体，C16H12O6.1H NMR (DMSO,500 MHz)δH:7.55(2H,d,J=7.2 Hz,H-2′,6′),6.91(2H,d,J=7.2 Hz,H-3′,5′),6.50(1H,s,H-8),6.18(1H,s,H-6).13C NMR(CD3COCD3,125 MHz)δC:147.2(s,C-2),135.9(s,C-3),176.0(s,C-4),160.3(s,C-5),97.4(d,C-6),164.9(s,C-7),92.1(d,C-8),156.1(s,C-9),104.0(s,C-10),121.6(s,C-1′),129.4(d,C-2′,6′),115.4(d,C-3′,5′),159.3(d,C-4′).以上数据与文献[14]报道基本一致，故鉴定6的结构为3,4′,5-trihydroxy-7-methoxyflavone.

化合物7白色晶体，C9H6O4.1H NMR (CD3COCD3, 400 MHz)δH:8.04(1H,d,J=6.0 Hz,H-2),6.20(1H,d,J=6.0 Hz,H-3),6.38(1H,d,J=2.3 Hz,H-8),6.24(1H,d,J=2.3 Hz,H-6).13C NMR(CD3COCD3,100 MHz)δC:155.6(d,C-2),111.4(d,C-3),181.9(s,C-4),162.3(s,C-5),98.2(d,C-6),165.6(s,C-7),92.8(d,C-8),158.1(s,C-9),106.7(s,C-10).以上数据与文献[15]报道基本一致，故鉴定7 的结构为5,7-dihydroxychromone.

化合物8白色无定型粉末，C30H48O3.ESI-MS:m/z471[M-H]-.1H NMR(400 MHz,DMSO)δH:0.79,0.81,0.91,0.94,0.98,1.02,1.15(Me×7),2.84(1H,dd,J=13.5,3.6 Hz),2.95(IH,d,J=9.5 Hz),3.65(1H,m,H-2),5.26(1H,brs,H-12).13C NMR(100 MHz,DMSO)δC:46.1(t,C-1),68.3(d,C-2),83.2(d,C-3),39.1(s,C-4),55.0(d,C-5),18.1(t,C-6),32.3(t,C-7),39.0(s, C-8),47.4(d, C-9),37.9(s,C-10),22.8(t,C-11),121.9(d,C-12),143.7(s,C-13),41.5(s,C-14),27.4(t,C-15),23.1(t,C-16),46.0(s,C-17),41.0(d,C-18),45.7(t,C-19),30.4(s,C-20),33.6(t,C-21),32.3(t,C-22),28.3(q,C-23),16.6(q,C-24),16.2(q,C-25),16.4(q,C-26),25.6(q,C-27),180.5(s,C-28),32.7(q,C-29),23.2(q,C-30).以上数据与文献[15]报道基本一致，故鉴定8的结构为maslinic acid.

化合物9白色无定型粉末，C30H50O.ESI-MS(m/z):457 [M+H ]+.1H NMR (CDCl3, 400 MHz)δH:5.20(1H,s,H-12),3.28(1H,dd,J=10.8,4.8 Hz,H-3α),1.04,1.02,0.96,0.87,0.84,0.82,0.79(Me×7);13C NMR(CDCl3,100 MHz)δc:145.2(s,C-13),121.8(d,C-12),79.1(d,C-3),55.3(d,C-5),47.7(d,C-9),47.3(d,C-18),46.9 (t, C-19),41.8(s,C-14),39.9(s,C-8),38.7(t,C-1),37.2(t,C-22),37.0(s,C-10),34.8(t,C-21),33.8(s,C-4),33.3(q,C-29)32.7(t,C-7),32.5(s,C-17),31.1(s,C-20),28.4(t,C-15),28.1(q,C-23),27.3(q,C-28),27.0(t,C-2),26.2(t,C-16),23.7(q,C-30),23.6(t,C-11),20.6(q,C-27),18.9(t,C-6),16.9(q,C-26),15.6(q,C-24),15.5(q,C-25).以上数据与文献[17]报道基本一致，故鉴定9的结构为β-amyrin.

化合物10白色无定型粉末，C30H48O2.ESI-MS(m/z):441 [M+H]+.1H NMR(CDCl3,400 MHz)δH:9.42(1H,s,H-28),5.31(1H,br s,H-12),3.31(1H,dd,J=9.5 Hz,H-3α),1.08,1.04,1.03,1.01,0.96,0.87,0.86(Me×7);13C NMR(CDCl3,100 MHz)δc:209.2(d,C-28),142.6(s,C-13),122.6(d,C-12),78.9(d,C-3),56.2(d,C-5),49.9(s,C-17),49.3(d,C-9),48.3(d,C-18),46.3(t,C-19),42.6(s,C-14),40.3(s,C-8),39.7(s,C-4),39.4(t,C-1),37.6(s,C-10),33.7(t,C-21),33.6(q,C-29),33.5(t,C-7),31.1(s,C-20),29.2(q,C-23),28.4(t,C-22),27.6(t,C-15),27.5(t,C-2),26.1(q,C-27),24.1(q,C-30),24.1(t,C-11),22.7(t,C-16),19.1(t,C-6),17.8(q,C-26),17.0(q,C-24),15.9(q,C-25).以上数据与文献[18]报道基本一致，故鉴定10的结构为oleanolic aldehyde.

化合物11白色无定型粉末，C30H48O3.ESI-MS(m/z):455 [M-H]-.1H NMR (CDCl3, 400 MHz)δH:5.31(1H,br s,H-12),3.31(1H,dd,J=9.2 Hz,H-3α),1.13,1.03,1.03,0.92,0.86,0.82,0.82,(Me×7);13C NMR(CDCl3,100 MHz)δc:180.8(d,C-28),138.1(s,C-13),125.4(d,C-12),78.8(d,C-3),55.8(d,C-5),48.1(d,C-9),46.7(s,C-17),46.5(d,C-18),42.2(s,C-14),42.0(t,C-19),39.8(s,C-8),39.4(s,C-4),38.9(t,C-1),37.4(s,C-10),34.2(t,C-21),33.3(q,C-29),33.3(t,C-22),33.2(t,C-7),31.0(s,C-20),28.3(q,C-23),28.3(t,C-15),28.1(t,C-2),26.2(q,C-27),23.8(q,C-30),23.7(t,C-16),23.1(t,C-11),18.8(t,C-6),17.4(q,C-26),16.5(q,C-24),15.6(q,C-25).以上数据与文献[18]报道基本一致，故鉴定11的结构为oleanolic acid.

化合物12白色晶体，C20H30O2.1H NMR(CDCl3,500 MHz)δH:6.88(1H,dd,J=2.7,4.5 Hz,H-14),6.19(1H,dd,J=15.5,17.5 Hz,H-16),5.12(1H,dd,J=15.5,17.5 Hz,H-16),4.62(1H,m,H-11),1.36,1.23,1.13,1.09(each 3H,s,Me×4).13C NMR(CDCl3,100 MHz)δC:36.9(t,C-1),18.5(t,C-2),41.8(t,C-3),33.2(s,C-4),49.6(d,C-5),38.3(t,C-6),200.1(s,C-7),130.9(s,C-8),54.3(d,C-9),36.2(s,C-10),66.5(d,C-11),39.3(t,C-12),42.6(s,C-13),144.4(d,C-14),146.6(d,C-15),111.4(t,C-16),27.7(q,C-17),32.9(q,C-18),21.4(q,C-19),16.7(q,C-20),以上数据与文献[19]报道基本一致，故鉴定12的结构为11-hydroxy-8(14),15-isopimaradien-7-one.

化合物13油状物，C9H14O4.1H NMR(CDCl3,500 MHz)δH:4.26(1H,dd,J=5.1,11.8 Hz,H-1),4.09(1H,dd,J=7.2,11.8 Hz,H-1),2.71(1H,dd,J=7.6,15.2 Hz,H-4),2.34(1H,dd,J=7.6,15.2 Hz,H-4),2.62(1H,m,H-5),3.98(1H,d,J=4.5 Hz,H-6),2.84(1H,m,H-9),1.33(3H,s,H-10).13C NMR(CDCl3,125 MHz)δC:67.2(t,C-1),173.5(s,C-3),32.2(t,C-4),44.3(d,C-5),78.6(d,C-6),48.0(t,C-7),81.1(s,C-8),45.8(d,C-9),22.7(q,C-10).以上数据与文献[20]报道基本一致，故鉴定13的结构为 jioglutolide.

化合物14油状物，C9H14O3.ESI-MS(m/z):171 [M+H]+.1H NMR (CDCl3,400 MHz)δH:4.99(1H,d,J=7.2 Hz,H-1),2.10(1H,m,H-4),1.78(1H,m,H-4),3.02(1H,m,H-5),2.92(1H,br. s,H-6),5.65(1H,br. s,H-8),4.28(1H,d,J=13.1 Hz,H-10),4.15(1H,d,J=13.1 Hz,H-10).13C NMR(CDCl3,100 MHz)δC:86.7(d,C-1),67.7(t,C-3),27.8(t,C-4),43.0(d,C-5),48.6(d,C-6),147.9(d,C-7),128.3(d,C-8),62.4(t,C-9),60.6(t,C-10).以上数据与文献[21]报道基本一致，故鉴定14的结构为 ningpogenin.

化合物15白色针状晶体，C28H42O3.ESI-MS(m/z):427[M+H]+,1H NMR (CDCl3，400 MHz)δH:6.48(1H,d,J=8.4 Hz,H-7),6.22(1H,d,J=8.4 Hz,H-6),5.42(1H,dd,J=2.0,6.0 Hz,H-11),5.19(1H,dd,J=15.0,7.2 Hz,H-23),5.10(1H,dd,J=15.0,7.2 Hz,H-22),3.94(1H,m,H-3),13C NMR(CDCl3,100 MHz)δC:34.6(t,C-1),30.1(t,C-2),66.4(d,C-3),36.9 (t, C-4),82.8 (s, C-5),135.4 (d,C-6),130.8 (d, C-7),79.4 (s, C-8), 142.6 (s, C-9), 37.0 (s, C-10), 119.8 (d, C-11), 39.3 (t, C-12),44.5 (s, C-13),51.6 (d, C-14), 20.6 (t, C-15), 28.6 (t, C-16),56.2 (d, C-17), 12.9 (q, C-18), 18.2 (q, C-19),39.7(d,C-20),20.9(q,C-21),135.5(d,C-22),134.4(d,C-23),42.7(d,C-24),33.0(d,C-25),19.8(q,C-26),19.6(q,C-27),17.5(q,C-28).以上数据与文献[11]报道基本一致，故鉴定15的结构为3β-hydroxy-5α,8α-epidioxyergosta-6,11,22-diene.

化合物16白色针状晶体，C28H44O3.ESI-MS(m/z):429[M+H]+；1H NMR(CDCl3，400 MHz)δ:6.48(1H,d,J=8.4 Hz,H-7),6.22(1H,d,J=8.4 Hz,H-6),5.19(1H,dd,J=15.0,7.2 Hz,H-23),5.10(1H,dd,J=15.0,7.2 Hz,H-22),3.94(1H,m,H-3),13C NMR(CDCl3,100 MHz),34.6(t,C-1),30.1(t,C-2),66.4(d,C-3),36.9(t,C-4),82.1(s,C-5),135.4(d,C-6),130.8(d,C-7),79.4(s,C-8),51.0(d,C-9),37.0(s,C-10),23.4(t,C-11),39.3(t,C-12),44.5(s,C-13),51.6(d,C-14),20.6(t,C-15),28.6(t,C-16),56.2(d,C-17),12.9(q,C-18),18.2(q,C-19),39.7(d,C-20),20.9(q,C-21),135.2(d,C-22),132.3(d,C-23),42.7(d,C-24),33.0(d,C-25),19.8(q,C-26),19.6(q,C-27),17.5(q,C-28). 以上数据与文献[22]报道基本一致，故鉴定16的结构为3β-hydroxy-5α,8α-epidioxyergosta-6,22-diene.

3 结果与讨论

本文运用现代分离分析技术研究了七里香的化学成分，从其乙酸乙酯部分分离鉴定18个单体化合物，其中1～3为芝麻素类，4～7为黄酮类，8～11为五环三萜类，12为二萜类，13～14为单萜类，15～16为甾体类，其中化合物1～3、6、7和12～15为首次从该植物中分离得到.