石松的化学成分研究
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摘要
目的研究石松全草的化学成分。方法石松全草采用80%的乙醇回流提取,乙醇提取物经过酸溶碱沉后,用乙酸乙酯进行萃取,乙酸乙酯相经过硅胶柱层析、中压制备液相色谱及HPLC等进行分离纯化,采用现代波谱技术结合理化性质鉴定化合物结构。结果从石松乙醇提取物中分离并鉴定了11个化合物,包括8个生物碱:α-异玉柏碱(1)、α-玉柏碱(2)、去-N-甲基-α-玉柏碱(3)、石松灵碱(4)、lycoposerramine M (5)、玉柏宁碱(6)、lyconadin D(7)、石松佛利星碱(8);2个三萜类化合物:石松三醇(9),α-芒柄花萜醇(10);1个酚苷类化合物:4-glucosyloxy-3-methoxyphenl trans-propenoic ethyl ester(11)。结论化合物1为新化合物,命名为α-异玉柏碱(α-isoobscurine)。化合物7和11为首次从该植物中分离得到。
OBJECTIVE To investigate the chemical constituents from the whole plant of Lycopodium japonicum.METHODS The whole plant of L.japonicum was refluxed with 80% ethanol.The concentrated extract was dissolved in 1% HCl solution.The supernatant was then basified and partitioned with EtOAc.The EtOAc fraction was chromatographed on silica gel column, purified by MPLC and preparative HPLC.The structures of isolated compounds were elucidated on the basis of spectroscopic data analyses.RESULTS Eleven compounds were isolated from the ethanolic extract of L.japonicum, including eight alkaloids: α-isoobscurine(1), α-obscurine(2), des-N-methyl-α-obscurine(3), lycodoline(4), lycoposerramine M(5), obscurinine(6), lyconadin D(7), and lycoflexine(8); two triterpenoids: lycoclavanol(9), α-onocerin(10); and a phenolic glycoside: 4-glucosyloxy-3-methoxyphenyl trans-propenoic ethyl ester(11).CONCLUSION Compound 1 is a new compound and named α-isoobscurine.Compounds 7 and 11 were isolated from this plant for the first time.
OBJECTIVE To investigate the chemical constituents from the whole plant of Lycopodium japonicum.METHODS The whole plant of L.japonicum was refluxed with 80% ethanol.The concentrated extract was dissolved in 1% HCl solution.The supernatant was then basified and partitioned with EtOAc.The EtOAc fraction was chromatographed on silica gel column, purified by MPLC and preparative HPLC.The structures of isolated compounds were elucidated on the basis of spectroscopic data analyses.RESULTS Eleven compounds were isolated from the ethanolic extract of L.japonicum, including eight alkaloids: α-isoobscurine(1), α-obscurine(2), des-N-methyl-α-obscurine(3), lycodoline(4), lycoposerramine M(5), obscurinine(6), lyconadin D(7), and lycoflexine(8); two triterpenoids: lycoclavanol(9), α-onocerin(10); and a phenolic glycoside: 4-glucosyloxy-3-methoxyphenyl trans-propenoic ethyl ester(11).CONCLUSION Compound 1 is a new compound and named α-isoobscurine.Compounds 7 and 11 were isolated from this plant for the first time.
引文
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[3]ZENG Y,YE M,XU H.Experimental studies on antiinflammation and analgesia pharmacological action of the diff erent extracts from Lycopodium japanicum L[J].Lishizhen Med Mater Med Res(时珍国医国药),1999,10(9):641-642.
[4]ZOU G,YOU X,LIU J,et al.Effects of extracts and active constituent from Lycopodium on platelet aggregation in rabbit[J].Asia-pacific Tradit Med(亚太传统医药),2012,8(11):10-11.
[5]LI M,LIU J,ZHANG Y,et al.Chemical constituents from whole herb of Lycopodium japonicum[J].Chin Tradit Herb Drug(中草药),2015,46(1):33-37.
[6]SHI L,HE Y.Serrantane Triterpenoid from Lycopodium japonicum[J].Chin J Exp Tradit Med Form(中国实验方剂学杂志),2012,18(9):90-92.
[7]滕翠翠,何永志,冯金磊,等.伸筋草的化学成分研究[J].中草药,2010,41(12):1960-1963.
[8]GE Y,SUN Q,WU J,et al.Alkaloids and triterpenoids from Lycopodium japonicum[J].J Hainan Norm Univ Nat Sci(海南师范大学学报-自然科学版),2016,29(3):277-281.
[9]NIU Y,CUI Y,YANG G,et al.Lycopodium alkaloids from Lycopodium japonicum[J].Chin Tradit Herb Drug(中草药),2015,46(9):1269-1276.
[10]LIU H,WANG Y.Study on chemical constituents of Lycopodium alkaloids[J].China J Chin Mater Med(中国中药杂志),2012,37(4):475-477.
[11]SUN Z H,LI W,TANG G H,et al.A new serratene triterpenoid from Lycopodium japonicum[J].J Asian Nat Prod Res,2017,19(3):299-303.
[12]ZHANG Y,YI P,CHEN Y,et al.Lycojaponicuminol A-F:cytotoxic serratene triterpenoids from Lycopodium japonicum[J].Fitoterapia,2014(96):95-102.
[13]YANG Q,ZHU Y,PENG W,et al.A new Lycopodine-type alkaloid from Lycopodium japonicum[J].Nat Prod Res,2016,30(19):2220-2224.
[14]WU J,WANG H,MA Y,et al.Isolation of a new lycodine alkaloid from Lycopodium japonicum[J].Nat Prod Res,2015,29(8):735-738.
[15]HE J,WU X D,LIU F,et al.Lycopodine-type alkaloids from Lycopodium japonicum[J].Nat Prod Bioprospect,2014,4(4):213-219.
[16]WANG X J,LI L,YU S S,et al.Five new fawcettimine-related alkaloids from Lycopodium japonicum Thunb[J].Fitoterapia,2013(91):74-81.
[17]WANG X J,LIU Y B,LI L,et al.Lycojaponicumins D and E:two new alkaloids from Lycopodium japonicum[J].Org Lett,2012,14(22):5688-5691.
[18]LI B,ZHANG W D,HE Y R,et al.New alkaloids from Lycopodium japonicum[J].Chem Pharm Bull,2012,60(11):1448-1452.
[19]WANG X J,ZHANG G J,ZHUANG P Y,et al.Lycojaponicumins A-C,three alkaloids with an unprecedented skeleton from Lycopodium japonicum[J].Org Lett,2012,14(10):2614-2617.
[20]HE J,CHEN X Q,LI M M,et al.Lycojapodine A,a novel alkaloid from Lycopodium japonicum[J].Org Lett,2009,11(6):1397-1400.
[21]AYER W A,KASITU G C.Some new Lycopodium alkaloids[J].Can J Chem,1989,67(6):1077-1086.
[22]TAKAYAMA H,KATAKAWA K,KITAJIMA M,et al.Ten new lycopodium alkaloids having the lycopodane skeleton isolated from Lycopodium serratum Thunb.[J].Chem Pharm Bull,2003,51(10):1163-1169.
[23]ISHIUCHI K,KUBOTA T,ISHIYAMA H,et al.Lyconadins D and E,and complanadine E,new Lycopodium alkaloids from Lycopodium complanatum[J].Bioorg Med Chem,2011,19(2):749-753.
[24]SETO H,FURIHATA K,GUANGYI X,et al.Assignments of the 1H-and 13C-NMR spectra of four lycopodium triterpenoids by the application of a new two-dimensional technique,heteronuclear multiple bond connectivity(HMBC)[J].Agr Bio Chem,1988,52(7):1797-1801
[25]PARK H B,LEE K H,KIM K H,et al.Lignans from the roots of Berberis amurensis[J].Nat Prod Sci,2009,15(1):17-21.