白叶香茶菜中的紫罗兰酮衍生物_英文_

白叶香茶菜中的紫罗兰酮衍生物

赵爱华

1,2

,彭丽艳1,王宗玉1

,孙汉董

1Ξ

(1中国科学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,云南昆明　650204;

2昆明医学院药学系,云南昆明　650031)

摘要:从白叶香茶菜Isodon leucophyllus (Dunn )K udo 地上部分的丙酮提取物中,分离得到1个新的紫罗兰酮类化合物和6个黄酮类化合物,经IR ,UV ,MS ,NMR 波谱数据分析,其结构分别确定为:13-羧基布卢姆醇C (1),5,7,3′,4′-四甲氧基黄酮(2),线蓟素(3),

5-羟基-6,7,3′,4′-四甲氧基黄酮(4),3′-羟基-5,7,8,4′-四甲氧基黄酮(5),

异甜橙素(6)和异槲皮素(7)。其中,化合物2-7均为首次从该植物中得到。关键词:白叶香茶菜;唇形科;13-羧基布卢姆醇C ;黄酮类化合物

中图分类号:Q 946 文献标识码:A 文章编号:0253-2700(2003)04-0503-04

An Ionone Derivative from Isodon leucophyllus

ZH AO Ai 2Hua

1,2

,PE NGLi 2Y an 1,W ANG Z ong 2Y u 1,S UN Han 2D ong

(1State K ey Laboratory o f Phytochemistry and Plant Resources in West China ,Kunming Institute o f Botany ,

Chinese Academy o f Sciences ,K unm ing 650204,China ;

2Department o f Pharmacology ,Kunming Medical College ,K unm ing 650031,China )

Abstract :A new ionone derivative and six known flav onoids were is olated from the aerial parts of Isodon leucophyllus (Dunn )K udo.Their structures were respectively elucidated as 132carboxy 2blumenol C (1),

5,7,3′,4′2tetramethoxy flav one (2),cirsiliol (3),52hydroxy 26,7,3′,4′2tetramethoxy flav one (4),3′2hydroxy 25,7,8,4′2tetramethoxy flav one (5),is osinensetin (6)and is oquercetrin (7),based on their spectra analysis.All of the six flav onoids were reported firstly from this plant.K ey w ords :Isodon leucophyllus ;Labiatae ;132carboxy 2blumenol C ;Flav onoids

Abundant diterpenoids in Isodon species have attracted the attentions of many phytochemists.H owever ,literatures about the non 2diterpenoids in genus Isodon have been seldom reported.Isodon leucophyllus (Dunn )K udo has been als o proved to be rich in diterpenoids (Chen et al ,1999;Liao et al ,1997,1998).In continuation of our research w ork on this plant collected in Zhongdian C ounty ,a new ionone derivative (1)and six known flav onoids (2-7)were obtained besides a large am ount of diterpenoids.This paper presents the is olation and structure elucidation of the new com 2pound.

云南植物研究　2003,25(4):503～506

Acta Botanica Yunnanica

ΞT o whom correspondence should be addressed.T el :86-871-5223251 Fax :86-871-5216343

E -mail :hdsun @mail.kib.ac.cb

收稿日期:2003-03-14,2003-04-03接受发表

作者简介:赵爱华(1965-)女,博士研究生,主要从事植物化学研究。

R esults and Discussion

C om pound 1has the m olecular formula C 13H 20O 4by negative 2ion high res olution FAB -MS (obsd 23911283,calcd 23911283).In the NMR spectra of 1,the characteristic signals of tw o tertiary methyls [δC 2718(q ),2813(q );δH

1103(3H ,s ),1101(3H ,s )],one secondary methyl [δC 2412(q ),δH 1130(3H ,d ,J =610H z )]and one qua 2ternary carbon [δC 3615(s )]were showed in high field ,together with thirteen carbons in its m

olecular formular ,indicat 2ing an ionone 2like skeleton of 1.An α,β2unsaturated m oiety deduced by the following spectral data :UV abs orption

Fig.1　The key H M BC (H →C )and ROESY (H ∴H )correlations of 1.

　λK Br max 240nm ,IR band at νK Br max 1774cm -1and 13

C NMR signals at δC 20013(s ),13010(d ),15519(s )and 1

H NMR signal at 7110(1H ,s ).From the H M BC

spectrum of 1,tw o AB spin system protons [

δH 2128,2168(each 1H ,d ,J =1712H z )]due to H 2-2showed cross peaks with the keto carbonyl carbon and the tw o tertiary methyl carbons which suggested the α,β2unsaturated m oiety at C

-5,C -4and C -3.C om paring the 13

C NMR data of 1with those of blumenol C (1a )(T oshio et al ,1988),the only difference is that a carb oxylic carb onyl carb on signal at δC 17014(s )was replaced by a methyl signal at δC 2415(q )in blu 2

men ol C ,which suggested that M e 213of 1a was oxidated into a carb oxylic group in 1.H M BC correlation from H -6[δH 2197

(1H ,t ,J =613H z )]to the carb oxylic carb on con firmed the ab ove deduction.H -6was determ ined as α2orientation on the

basis of R OESY correlation between H -7[δH 2131(1H ,m )]and H 3-11[δH 1101(3H ,s )].T

he relative stereochem istry of C -9was generally considered to be same as that of blumen ol C ,judging from very sim ilar

C N MR data at C -8,C -9

and C -10,and positive rotation values in b oth com pounds.T hus ,1was elucidated as 132carboxy blumenol C.

C om pounds 2-7were determined as 5,7,3′,4′2tetrameth oxy flav one 2(Chien et al .,1984),cirsiliol (5,3′,4′2trihydroxy 26,72dimeth oxy flav one )3(Shin et al ,1973),52hydroxy 26,7,3′,4′2tetrameth oxy flav one 4(K arl et al ,1989),3′2hydroxy 25,7,8,4′2tetrameth oxy flav one 5(Z h ong et al ,1984),is osinensetin (5,7,8,3′,4′2pentame 2

th oxy flav one )6(G eorge et al ,1984)and is oquercetrin (32O 2β2D 2glucopyranosyl 25,7,3′,4′2tetrahydroxy flav one )7

(Wahono et al ,1991)respectively by com paring their spectral data with those reported in literatures.

Experimental

G eneral Optical rotation was recorded on a SEPA -300polarimetre.UV spectrum was obtained on a UV 210-A spectrometer.IR spectrum was measured on a Bio 2Rad FTS -135spectrometer with K Br pellets.1D and 2D NMR spec 2

05 云　南　植　物　研　究 25卷

tra were taken on a Bruker AM -400and DRX -500instrument with T MS as internal standard ,respectively.

P lant Material The aerial parts of I 1leucophyllus were collected in Zhongdian C ounty ,northwest of Y unnan Prov 2ince in October 2001,and were identified by Profess or Li X i 2Wen.The v oucher specimen (KI B 01-10-183)is depos 2ited in Laboratory of Phytochemistry ,K unming Institute of Botany ,Chinese Academy of Sciences.

Extraction and isolation The dried and powdered aerial plants (211kg )were extracted with 70%aq.acetone at room tem perature for 4×24h.The extract was concentrated in vacuo and filtered to rem ove pigment ,then the filtrate was partitioned between E tOAc and H 2O.The E tOAc extract (57g )was subjected to column chromatograph over silica gel and eluted with CHCl 3ΠMe 2C O (from 1∶0to 0∶1)to give seven fractions.Then com pounds 2(30mg ),3(45mg ),4(70mg ),5(120mg )and 6(24mg )were purified from the CHCl 3ΠMe 2C O (9∶1)fraction ,1(14mg )and 7(840mg )were obtained from the CHCl 3ΠMe 2C O (6∶4)fraction after repeatly column chromatograph.

T able 1　1

H and

C NMR spectral data for 1and 1a 3

position 1

δC δH

3615s 3612s 24715t 2128(d ,1712),2168(d ,1712)4712t 2103(d ,17),2137(d ,17)320013s 19912s 413010d 7110(s )12511d 5182(s )

515519s 16513s 64512d 2197

(t ,613)

5111d 72813t 1167(m ),2131(m )2613t 83819t 1188(m ),1196(m )3817t 96713d 4100(m )

6812d 3175

(m )

102412q 1130(d ,610)2316q 1120(d ,610)112718q 1101(s )2710q 1102(s )122813q 1103

(s )

2818q 1107(s )13

17014s

2415q

2100(s )

　3measured in CDCl 3(T oshio et al ,1988)

Compound 1,colorless gum ,C 13H 20O 4,[α]25D =+57176(c 0129,MeOH );UV λK Br max (lg ε):218(3198),240(3183)nm ;IR νK Br max :3439,1774,1645cm -1;FAB MS (negative )m Πz (%):239[M -H]+

(100);EI MS (70eV )m Πz (%):222[M -H 2O]

(54),207(14),195(21),179(24),168(35),153(22),138(33),123(45),109(40),93(79),79(24);

H NMR and

C NMR data (in C 5

D 5N )see T able 1.

Compound 2,yellow crystals ,C 19H 18O 6,13

C NMR (100MH z ,DMS O 2d 6)δ:16112(s ,C -2),10813(d ,

C -3),17615(s ,C -4),15215(s ,C -5),9617(d ,C -6),16413(s ,C -7),9317(d ,C -8),15215(s ,C -9),10813(s ,C -10),12415(s ,C -1′

),10918(d ,C -2′),16011(s ,C -3′),16016(s ,C -4′),11211(d ,C -5′),11919(d ,C -6′),5611,5610,5518and 5517(each q ,OCH 3);

H NMR (400MH z ,DMS O 2d 6)

δ:7165(1H ,dd ,J =814,212H z ,H -6′),7157(1H ,d ,J =212H z ,H -2′),7106(1H ,br d ,J =814

H z ,H -5′

),6185(1H ,d.J =213H z ,H -8),6170(1H ,s ,H -3),6155(1H ,d ,J =213H z ,H -6),3184,3182,3179and 3178(each 3H ,s ,OCH 3);EI MS m Πz (%):342[M]

(100),325(20),313(42),296(45),281(6),269(8),241(7),226(7),162(15).

Compound 3,yellow crystals ,C 17H 14O 7,

C NMR (100MH z ,DMS O 2d 6)δ:16511(s ,C -2),10315(d ,

C -3),18219(s ,C -4),15219(s ,C -5),13217(s ,C -6),15914(s ,C -7),9212(d ,C -8),15314(s ,C -9),10519(s ,C -10),12214(s ,C -1′

),11413(d ,C -2′),14616(s ,C -3′),15017(s ,C -4′),11619(d ,C -5′),11919(d ,C -6′),6019and 5712(each q ,OCH 3);

H NMR (400MH z ,DMS O 2d 6)δ:7139(1H ,

s ,H -2′

),7138(1H ,d ,J =810H z ,H -6′),6189(1H ,d ,J =810H z ,H -5′),6174(1H ,s ,H -8).6163(1H ,s ,H -3),3187and 3171(each 3H ,s ,OCH 3);EI MS m Πz (%):328[M -2H]

(100),313(77),5054期赵爱华等:白叶香茶菜中的紫罗兰酮衍生物

605 云　南　植　物　研　究 25卷

299(18),285(16),268(6),180(15),152(31),133(12),68(20).

Compound4,yellow crystals,C19H18O7,13C NMR(100MH z,DMS O2d6)δ:16410(s,C-2),10414(d,C-3),18215(s,C-4),15312(s,C-5),13217(s,C-6),15817(s,C-7),9016(d,C-8),15312(s,C-9), 10611(s,C-10),12318(s,C-1′),11112(d,C-2′),14913(s,C-3′),15213(s,C-4′),10818(d,C-5′), 12011(d,C-6′),6018,5613,5611and5610(each q,OCH3);1H NMR(400MH z,DMS O2d6)δ:7150(1H,dd, J=814,116H z,H-6′),7131(1H,d,J=116H z,H-2′),6196(1H,d,J=814H z,H-5′),6158(1H, s,H-8).6153(1H,s,H-3),3197,3196,3195and3191(each3H,s,OCH3);EI MS mΠz(%):356[M-2H]+(100),341(85),327(20),313(17),297(6),280(4),255(5),180(7),162(15),152(37).

Compound5,yellow crystals,C19H18O7,13C NMR(100MH z,DMS O2d6)δ:16116(s,C-1),10619(d, C-3),17618(s,C-4),15215(s,C-5),9811(d,C-6),15814(s,C-7),14017(s,C-8),15419(s,C -9),11218(s,C-10),12411(s,C-1′),11218(d,C-2′),14716(s,C-3′),15116(s,C-4′),11316 (d,C-5′),11911(d,C-6′),6218,6210,5714and5617(each q,OCH3);1H NMR(400MH z,DMS O2d6)δ:7130(1H,br d,J=815H z,H-6′),7121(1H,s,H-2′),6196(1H,s,H-6),6188(1H,br d,J= 815H z,H-5′),6139(1H,s,H-3),3175,3167,3160and3157(each3H,s,OCH3);EI MS mΠz(%):356 [M-2H]+(34),341(100),326(11),311(13),294(11),267(4),180(2).

Compound6,yellow crystals,C20H20O7,1H NMR(400MH z,DMS O2d6)δ:7168(1H,br d,J=814H z, H-6′),7161(1H,br s,H-2′),7113(1H,s,H-3),7108(1H,br d,J=814H z,H-5′),7101(1H,s, H-6),4117,3193,3183,3181and3180(each3H,s,OCH3);EI MS mΠz(%):372[M]+(52),357(100), 341(28),313(9),282(4),195(7),179(8),167(28).

Compound7,yellow crystals,C21H20O12,1H NMR(400MH z,DMS O2d6)δ:7157(1H,d,J=818H z,H -6′),7156(1H,s,H-2′),6183(1H,d,J=818H z,H-5′),6139(1H,d,J=210H z,H-8),6119 (1H,d,J=210H z,H-6),5144(1H,d,J=713H z,H-1″);F A BMS(negative)mΠz(%):463[M-H]+ (100),301(47);EI MS(%)mΠz:302(100),286(8),273(15),245(9),229(9),153(13),137(20).

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