崔小燕，劉亞平，衣 振，程桂廣

(1.昆明醫(yī)科大學(xué)海源學(xué)院, 云南 昆明 650106；2.昆明理工大學(xué) 農(nóng)業(yè)與食品學(xué)院，云南 昆明 650500;3.山東職健檢測(cè)技術(shù)有限公司，山東 聊城 252000)

醉魚(yú)草屬(Buddleja)是馬錢(qián)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(qū)，我國(guó)醉魚(yú)草屬植物資源豐富，約有29個(gè)種.該屬植物許多種具有觀賞和藥用價(jià)值，具有較強(qiáng)的生物活性，在世界很多地區(qū)作為傳統(tǒng)用藥.七里香(BuddlejaasiaticaLour)，為馬錢(qián)科醉魚(yú)草屬植物，直立灌木或亞灌木，生于海拔200～3 000 m 的向陽(yáng)山坡灌木叢中或疏林緣.全草藥用，有驅(qū)風(fēng)化濕、行氣活絡(luò)之功效，用于治療發(fā)燒、疼痛、痢疾和關(guān)節(jié)炎[1].

對(duì)醉魚(yú)草屬植物的化學(xué)成分研究較多，報(bào)道的結(jié)構(gòu)類型多為三萜及其苷[2-3]、黃酮及其苷[4]、環(huán)烯醚萜苷[5]、倍半萜烯[6]、二萜[7]及皂苷[8].但對(duì)七里香(B.asiatica)化學(xué)成分的報(bào)道較少，對(duì)其甲醇提取物乙酸乙酯萃取部分進(jìn)行分離，得16個(gè)化合物，通過(guò)核磁共振、質(zhì)譜及相應(yīng)文獻(xiàn)鑒定結(jié)構(gòu)：(-)-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(shí)驗(yàn)部分

1.1 材料與儀器

Bruker DRX - 500核磁共振波譜儀(德國(guó)Bruker公司)；VG Autospec-3000電子轟擊質(zhì)譜；EYELA OSB-2100旋轉(zhuǎn)蒸發(fā)儀(上海愛(ài)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(xué)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(jié)構(gòu)圖

七里香(B.asiatica)采自中國(guó)廣西，由曾春霞博士鑒定，標(biāo)本存放在中科院昆明植物研究所植物化學(xué)與西部植物資源持續(xù)利用國(guó)家重點(diǎn)實(shí)驗(yàn)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(jīng)硅膠柱層析(CHCl3-Me2CO 1∶0～1∶1)，TLC檢測(cè)合并得6個(gè)組分(Ⅰ～Ⅵ).組分Ⅱ(54 g)經(jīng)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(jīng)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(jīng)RP-18反相柱層析(體積分?jǐn)?shù),甲醇∶水=60%～90%)，再經(jīng)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(jīng)RP-18反相柱層析(體積分?jǐn)?shù)，甲醇∶水=60%～90%)得Ⅲ-1～Ⅲ-4.Ⅲ-4(1 g)經(jīng)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(jīng)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(jīng)RP-18反相柱層析(體積分?jǐn)?shù)，甲醇∶水=40%～80%)，再經(jīng)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(jīng)過(guò)RP-18反相柱層析(體積分?jǐn)?shù)，甲醇∶水=30%～70%)，再經(jīng)凝膠柱層析(甲醇)得4(9 mg)和6(198 mg).組分Ⅵ(3 g)經(jīng)硅膠柱層析(體積比,氯仿∶甲醇=10∶1～2∶1)，再經(jīng)中壓柱層析(體積分?jǐn)?shù)，甲醇∶水=30%～60%)，再經(jīng)凝膠柱純化(甲醇)得13(90 mg)和14(36 mg).

2 結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[9]報(bào)道基本一致，故鑒定1的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[10]報(bào)道基本一致，故鑒定2的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[11]報(bào)道基本一致，故鑒定3的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[12]報(bào)道基本一致，故鑒定4的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[13]報(bào)道基本一致，故鑒定5的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[14]報(bào)道基本一致，故鑒定6的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[15]報(bào)道基本一致，故鑒定7 的結(jié)構(gòu)為5,7-dihydroxychromone.

化合物8白色無(wú)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(shù)據(jù)與文獻(xiàn)[15]報(bào)道基本一致，故鑒定8的結(jié)構(gòu)為maslinic acid.

化合物9白色無(wú)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(shù)據(jù)與文獻(xiàn)[17]報(bào)道基本一致，故鑒定9的結(jié)構(gòu)為β-amyrin.

化合物10白色無(wú)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(shù)據(jù)與文獻(xiàn)[18]報(bào)道基本一致，故鑒定10的結(jié)構(gòu)為oleanolic aldehyde.

化合物11白色無(wú)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(shù)據(jù)與文獻(xiàn)[18]報(bào)道基本一致，故鑒定11的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[19]報(bào)道基本一致，故鑒定12的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[20]報(bào)道基本一致，故鑒定13的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[21]報(bào)道基本一致，故鑒定14的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[11]報(bào)道基本一致，故鑒定15的結(jié)構(gòu)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(shù)據(jù)與文獻(xiàn)[22]報(bào)道基本一致，故鑒定16的結(jié)構(gòu)為3β-hydroxy-5α,8α-epidioxyergosta-6,22-diene.

3 結(jié)果與討論

本文運(yùn)用現(xiàn)代分離分析技術(shù)研究了七里香的化學(xué)成分，從其乙酸乙酯部分分離鑒定18個(gè)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(huán)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.