七里香的化學成分研究

崔小燕，劉亞平，衣 振，程桂廣

(1.昆明醫科大學海源學院, 云南 昆明 650106；2.昆明理工大學 農業與食品學院，云南 昆明 650500;3.山東職健檢測技術有限公司，山東 聊城 252000)

醉魚草屬(Buddleja)是馬錢科中最大的屬，多為灌木，少有喬木和亞灌木狀草本，分布于美洲、非洲和亞洲的熱帶至溫帶地區，我國醉魚草屬植物資源豐富，約有29個種.該屬植物許多種具有觀賞和藥用價值，具有較強的生物活性，在世界很多地區作為傳統用藥.七里香(BuddlejaasiaticaLour)，為馬錢科醉魚草屬植物，直立灌木或亞灌木，生于海拔200～3 000 m 的向陽山坡灌木叢中或疏林緣.全草藥用，有驅風化濕、行氣活絡之功效，用于治療發燒、疼痛、痢疾和關節炎[1].

對醉魚草屬植物的化學成分研究較多，報道的結構類型多為三萜及其苷[2-3]、黃酮及其苷[4]、環烯醚萜苷[5]、倍半萜烯[6]、二萜[7]及皂苷[8].但對七里香(B.asiatica)化學成分的報道較少，對其甲醇提取物乙酸乙酯萃取部分進行分離，得16個化合物，通過核磁共振、質譜及相應文獻鑒定結構：(-)-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](圖1).

1 實驗部分

1.1 材料與儀器

Bruker DRX - 500核磁共振波譜儀(德國Bruker公司)；VG Autospec-3000電子轟擊質譜；EYELA OSB-2100旋轉蒸發儀(上海愛朗儀器有限公司)；中壓分離裝置(瑞士步琦有限公司)；薄層層析硅膠板(青島譜科有限公司)；葡聚糖凝膠Sephadex LH-20(Pharmacia化學公司)；RP-C18gel (Merck公司)；色譜甲醇、乙腈(Merck公司)；化合物先在熒光燈UV (254、365 nm)下觀察，后噴灑含有茴香醛的硫酸乙醇溶液，最后 100 ℃ 加熱5～10 min.

圖1 七里香中化合物1～16結構圖

七里香(B.asiatica)采自中國廣西，由曾春霞博士鑒定，標本存放在中科院昆明植物研究所植物化學與西部植物資源持續利用國家重點實驗室.

1.2 提取與分離

七里香(B.asiatica)樣品(8.5 kg)曬干粉碎，甲醇室溫浸提4 d，減壓濃縮乙酯萃取4次，得浸膏(130 g)，經硅膠柱層析(CHCl3-Me2CO 1∶0～1∶1)，TLC檢測合并得6個組分(Ⅰ～Ⅵ).組分Ⅱ(54 g)經硅膠柱層析(體積比，石油醚∶丙酮=30∶1～10∶1)得Ⅱ-1～Ⅱ-5.Ⅱ-2(8 g)經硅膠柱分離(體積比，石油醚∶乙酸乙酯=10∶1～2∶1)得到12(5 mg)和1(6 mg).Ⅱ-3(10 g)經RP-18反相柱層析(體積分數,甲醇∶水=60%～90%)，再經凝膠柱層析(體積比，甲醇∶氯仿=1∶1)得2(126 mg)，3(2 mg) 和8(43 mg).組分Ⅲ(20 g)經RP-18反相柱層析(體積分數，甲醇∶水=60%～90%)得Ⅲ-1～Ⅲ-4.Ⅲ-4(1 g)經硅膠柱(體積比，石油醚∶乙酯=12∶1,7∶1，5∶1)洗脫得9(40 mg)和10(23 mg).Ⅲ-3(5 g)經硅膠柱(體積比，石油醚∶乙酯=12∶1～1∶1)純化得15(20 mg)和16(76 mg).組分Ⅳ(21 g)經RP-18反相柱層析(體積分數，甲醇∶水=40%～80%)，再經硅膠柱(體積比，石油醚∶乙酯=12∶1～1∶1)洗脫得11(52 mg)，7(14 mg) 和5(15 mg).組分Ⅴ(20 g)經過RP-18反相柱層析(體積分數，甲醇∶水=30%～70%)，再經凝膠柱層析(甲醇)得4(9 mg)和6(198 mg).組分Ⅵ(3 g)經硅膠柱層析(體積比,氯仿∶甲醇=10∶1～2∶1)，再經中壓柱層析(體積分數，甲醇∶水=30%～60%)，再經凝膠柱純化(甲醇)得13(90 mg)和14(36 mg).

2 結構鑒定

化合物1黃色晶體，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).以上數據與文獻[9]報道基本一致，故鑒定1的結構為(-)-diasesamin-di-γ-lactone.

化合物2白色晶體，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-).以上數據與文獻[10]報道基本一致，故鑒定2的結構為(-)-aptosimon.

化合物3白色針狀晶體，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).以上數據與文獻[11]報道基本一致，故鑒定3的結構為 (+)-sesamin.

化合物4黃色晶體，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).以上數據與文獻[12]報道基本一致，故鑒定4的結構為luteolin.

化合物5黃色晶體，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′).以上數據與文獻[13]報道基本一致，故鑒定5的結構為 5,7-dihydroxyflavone.

化合物6黃色晶體，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′).以上數據與文獻[14]報道基本一致，故鑒定6的結構為3,4′,5-trihydroxy-7-methoxyflavone.

化合物7白色晶體，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).以上數據與文獻[15]報道基本一致，故鑒定7 的結構為5,7-dihydroxychromone.

化合物8白色無定型粉末，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).以上數據與文獻[15]報道基本一致，故鑒定8的結構為maslinic acid.

化合物9白色無定型粉末，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).以上數據與文獻[17]報道基本一致，故鑒定9的結構為β-amyrin.

化合物10白色無定型粉末，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).以上數據與文獻[18]報道基本一致，故鑒定10的結構為oleanolic aldehyde.

化合物11白色無定型粉末，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).以上數據與文獻[18]報道基本一致，故鑒定11的結構為oleanolic acid.

化合物12白色晶體，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),以上數據與文獻[19]報道基本一致，故鑒定12的結構為11-hydroxy-8(14),15-isopimaradien-7-one.

化合物13油狀物，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).以上數據與文獻[20]報道基本一致，故鑒定13的結構為 jioglutolide.

化合物14油狀物，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).以上數據與文獻[21]報道基本一致，故鑒定14的結構為 ningpogenin.

化合物15白色針狀晶體，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).以上數據與文獻[11]報道基本一致，故鑒定15的結構為3β-hydroxy-5α,8α-epidioxyergosta-6,11,22-diene.

化合物16白色針狀晶體，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). 以上數據與文獻[22]報道基本一致，故鑒定16的結構為3β-hydroxy-5α,8α-epidioxyergosta-6,22-diene.

3 結果與討論

本文運用現代分離分析技術研究了七里香的化學成分，從其乙酸乙酯部分分離鑒定18個單體化合物，其中1～3為芝麻素類，4～7為黃酮類，8～11為五環三萜類，12為二萜類，13～14為單萜類，15～16為甾體類，其中化合物1～3、6、7和12～15為首次從該植物中分離得到.