全 文 ：Received date:2004-04-02
Foundation item:This work was partially supported by the Ministry of Science and Technology grant 2001-51;the Na-
tio nal Science Foundation of China(30070007);Chinese Academy of Sciences(KSCX2-SW-313)and
Natural Science Foundation of Yunnan Province(99B0017G)
Biographies:ZHAO Pei-ji(1974-),male(Bai nationality), w as born in Yunnan Province , a Master of Kunming Institute
of Botany , Chinese Academy of Sciences;SHEN Yue-mao(1965-),male(Han nationality), was bo rn in An-
hui P rovince , professor , and w as majo r in natural products of chemistry , Tel:(0871)5223111 , E-mail:yshen@
mail.kib.ac.cn.
Article ID:1005-0108(2004)05-0287-04
Identification of chemical constituents of the seed crusts
from Trewia nudif lora L.
ZHAO Pei-ji ,ZHU Na , SHEN Yue-mao
(The State Key Laboratory of Phytochemistry and Plant Resources in West China , K unming
Insti tute of Botany , Chinese Academy of Sciences ,K unm ing 650204 , China)
Abstract:Aim To study the chemical constituents of the seed crusts from Trewia nudif lora L.Method
F ive compounds were confirmed by the physical and chemical proper ties and the data of spectra.Result
and conclusion The structures of the five compounds were isolated from the seed crusts of Trewia nudi-
flora and determined to be 2 , 3-dihydro-3 , 6 , 7-trihydroxy-1-H-benzo[ b] py ran-4-one(1), α, 2′, 4 , 4′- te-
trahydroxydidro chalaone(2), isoliquiritigenin(3), 3-(3 , 4-dihydroxypheny l)-prop-2-en-1-ol(4), β-sitos-
terol(5).Among tho se , compound 1 w as determined to be a new compound , named nudiflone.Compound
3 showed antibacterial activity.
Key words:medicinal chemistry;isolation;identification;chromatog raphy;Trewia nudif lora L.;nudifone
CLC number:R284.1　　　Document code:A
　　Antimicrobial resistance is vi rtually emerging
in all the nosocomial pathogen-antimicrobial combi-
nat ions ,which highlights the need to stimulate fur-
ther research on strategies aimed at preserving the
effectiveness of current ly available ant ibacterial a-
gents and finding new classes of antibacterial a-
gents.Natural products produced by higher plants
evolved f rom selection for acquisi tion of the im-
proved defense against microbial at tacks
[ 1] , there-
fore , are less likely to incur resistance.
The genus Trewia(Euphorbiaceae)included
only one species , spread in India ,Malaysia and Chi-
na.Some maytansinoids isolated f rom the Trewia
nudi f lora seeds were tumo r inhibi tors
[ 2 , 3] .The
seeds of T .nudi f lora could be stored fo r several
years under normal conditions , so the seed crusts of
T .nudi f lora must be resistant to soil microorg an-
isms and fast rot.However , there w as no report
about the isolation of antibacterial components from
the seeds of T .nudi f lora , especially from the seed
crusts.The isolation , structure identification and
the antibacterial activities against g ram-positive
bacterium S taphylococcus aureus and g ram-nega-
tive bacterium Mycobacterium tuberculosis of the
chemical consti tuents of the seed crusts of T .nud-
i f lora are reported here.
1　Experiment
Optical rotations were measured on a JASCO DIP
-370 Digital Polarimeter.The IR spectra were mea-
sured on a Perkin-Dlmer-577 spectrophotometer.UV
spectra were obtained on a Shimadzu double-beam
210A spectrophotometer.The NMR spectra were
recorded on Brucker DRX -500 spectrometers.MS
were performed on a VG AutoSpec-3000 spectrometer.
TLC was performed on plates precoated with silica gel
第 14 卷　第 5 期
2004 年10月　总61 期
中 国 药 物 化 学 杂 志
Chinese Journal o f Medicinal Chemistry
Vol.14　No.5　p.287
Oct.2004 Sum 61
DOI :10.14142/j.cnki.cn21-1313/r.2004.05.008
(Qingdao Marine Chemical Co., Ltd., The People′s
Republic of China).Reversed-phase(RP)C18 silica gel
for column chromatography w as obtained from Merck.
Sephadex LH-20 for column chromatography was pur-
chased from Amersham Biosciences.The solvents were
distilled before using.
1.1　Extraction and isolation
The seeds of T .nudi f lora were collected at
Xishuangbanna , Yunnan Province , The People′s
Republic of China , in December 1998.The seed
crusts of T .nudi f lora(dry w eight:6.5 kg)were
ex tracted three times wi th 70%(φ)ethanol.The
ethanol ext ract w as po rt ioned between acetyl ac-
etate and w ater.The acety l acetate ex tract w as ex-
tracted w ith pet roleum ether(PE)and chloroform
(CH)to produce tw o fractions:PE and CH.Frac-
tion CH(105 g)was chromatog raphed on silica
gel ,RP-18 and Sephadex LH-20 column to produce
compounds 1(11 mg), 2(3 mg), 3(5 mg), 4
(42 mg).The fraction PE(152 g)was chro-
matog raphed on silica gel column and recrystallized
from acetone to af ford compound 5(200 mg).
1.2　Physical and spectral data
Compound 1 , yellow powder , [ α] 23D -8.0°(c
0.50 , MeOH).UV(MeOH)λmax :210 , 238 , 279 ,
340 nm.EIMS m/ z(%):196[ M ] +(66), 152
(100),124(28),82(43).IR(KBr)σ:3406 , 1664 ,
1622 , 1586 , 1518 , 1477 , 1454 , 1289 , 1167 cm-1.
see 1H- and 13C-NMR data in Table 1.
Table 1　The NMR data of compound 1 in CD3OD
Position 13C 1H HMBC
2 72.3 4.73(dd , J=5.3 , 10.5 Hz) 69.9 , 158.1 , 193.1
4.45[ t(dd), J=10.7 Hz] 69.9 , 158.1(w), 193.1
3 69.9 4.78(dd , J=5.2 , 10.7 Hz) 72.3 , 158.1 , 193.1
4 193.1
9 112.5
5 111.9 7.91(s) 143.2 , 156.4 , 158.1 , 193.1 , 104.3(w)
6 143.2
7 156.4
8 104.3 6.88(s) 112.5 , 143.2 , 158.1 , 156.4
10 158.1
　　Compound 2 , yellow needle(MeOH).EIMS
m/ z(%):256[ M -H2O ] +(78), 239(10), 163
(25), 137(100), 120(67), 91(19).1H-NMR
(400 MHz , MeOD)δ:2.71(1H , d , J =16.9 Hz),
3.08(1H , t , J =13.1 Hz), 6.35(1H , s , H-3′),
6.50(1H ,dd , J =8.7 ,2.1 Hz ,H-2),6.81(2H ,d ,
J =8.9 Hz , H-2 , H-6), 7.32(2H , d , J =8.9 Hz ,
H-3 ,H-5), 7.73(1H , d , J =8.7 Hz ,H-6′).Those
data w ere consistent with literature[ 4] , therefo re ,
compound 2 was determined to be α, 2′, 4 , 4′-te-
trahydroxydihydrochalcone.
Compound 3 , yellow oil.EIMS m/ z(%):256
—288— 中 国 药 物 化 学 杂 志 14卷
[M ] +(100), 255(75), 239(17), 192(4), 150
(25),163(41), 137(93), 120(42), 91(22),77(6).
Those data were consistent w ith literature
[ 5] ,
therefore , compound 3 was determined to be
isoliqui ritigenin.
Compound 4 , yellow crystal(MeOH).EIMS
m/ z(%):164[ M] +(100),147(49), 136(25), 77
(17).1H-NMR(400 MHz , CDCl3)δ:6.57(1H , dd ,
J =15.6 ,10.1 Hz ,H-8),6.82(1H ,d , J =8.2 Hz ,H-
5),7.05(1H ,dd , J =8.2 ,2.1 Hz ,H-6),7.12(1H ,
d , J =2.1 Hz ,H-2),7.54(1H ,d , J =15.7 Hz ,H-7),
9.56(1H , d , J =11.9 Hz ,H-9).Those data w ere
very much characteristic of caffeic esters[ 6] , so com-
pound 4 was determined to be 3-(3 , 4-dihydrox-
yphenyl)-prop-2-en-1-ol.
Compound 5 , colo rless needle(acetone).EIMS
m/ z(%):414[ M] +(100), 396(M -H 2O , 27),
381(18), 367(37),354(5),329(20),303(34),289
(5), 273(15), 255(15), 231(12), 213(16), 145
(17), 109(14)and 69(25).Comparing with the
standard sample on TLC over silica gel , compound
5 was determined to be β-sitosterol.
1.3　Antibacterial activity
The screening of compounds 1 ～ 4 for the an-
tibacterial activities w as assayed against Staphylo-
coccus aureus and Mycobacterium tuberculosis us-
ing the paper disc dif fusion method[ 7] .The results
showed that compound 3 had modest inhibi tory ac-
tivi ties against S .aureus and M .tuberculosis
(Table 2).
Table 2　Antimicrobial activities of compounds 1 ～ 4 and controls mm
Test organisms
Compounds
1　　2　　3　　4
(100 μg/ disk)
Controls
carbenicillin sodium
(10 μg/ disk)
streptomycin sulfate
(10 μg/disk)
rifampicin
(0.2 μg/ disk)
M.tuberculosis - - 6.5 - 15.0 11.0 15.0
S.aureus - - 6.5 - 12.0 10.0 15.0
　　Note:The data are the mean of the three replicates
2　Result and discussion
Compound 1 , the HRESIMS indicated the
molecular formula to be C9H8O5(m/ z 219.0262
[M +Na] + , calcd.219.0269).The IR spect ra
showed that 1 had a benzene ring(1586 , 1477 , 1518
cm-1), which w as supported by the UV spect ra
(λmax 238 nm).The spect ra of 1H- and 13C-NMR
data showed that 1 had one methylene , three me-
thines and five quaternary carbons , including one
carbony l g roup , indicating the presence of a sym-
metric four-substi tuted benzene ring [ δC:158.1
(s), 156.4(s), 143.2(s), 112.5(s), 111.9(d),
104.3(d);δH :7.91(s), 6.88(s)] .The conjugate
effect w hich was observed in the NMR with the
chemical shift at δC:193.1(s)and IR abso rption at
1664 cm-1 indicating the linkage of the carbonyl
functional group wi th the benzene ring.The struc-
ture of the pyranone w as elucidated based on the
HMBC betw een the methylene protons at δ4.73
(H-2)and the carbon at δ69.9(C-3), 158.1(C-
10)and 193.1(C-4), and the correlations between
the methine proton at δ4.78(H-3)and the car-
bons at δ72.3(C-2), 158.1(C-10)and 193.1(C-
4).Therefore , compound 1 was determined to be
2 , 3-dihydro-3 , 6 , 7-trihydroxy-1-H-benzo [ b ]
pyran-4-one , a new compound named nudiflone.
Acknowledgments:The authors are g rateful to M r.HE
YN and Ms.LIANG HL in the State Key Laboratory of
Phy tochemistry and Plant Resources in West China , Kun-
ming Institute of Bo tany , Chinese Academy of Sciences , fo r
measuring NM R and MS data , respectively.
References:
[ 1] 　Dixon RA.Natural products and plant disease resis-
tance[ J] .Nature , 2001 , 411(14):843-847.
[ 2] 　Powell RG , Weisleder D , Smith CR Jr.Novel may-
tansinoid tumo r inhibitors from Trewia nudiflora:
trewiasine, dehydro trew iasine , and demethyltrewiasine
[ J] .J Org Chem , 1981 , 46(22):4398-4403.
[ 3] 　Pow ell RG , Weisleder D , Smith CR Jr , et al.T re-
florine , trenudine , and N-methyltrew iasine:novel
may tansinoid tumor inhibito rs containing two fused
macrocyclic rings[ J] .J Am Chem Soc , 1982 , 104
—289—5 期 ZHAO Pei-ji et al:Identification of chemical constituents of the seed crusts from Trew ia nudif lora L.
(18):4929-4934.
[ 4] 　Fer rari F , Botta B , de Lima RA.F lavonoids and
isoflavonoids from Zollernia paraensis [ J] .Phyto-
chemistry , 1983 , 22(7):1663-1664.
[ 5] 　Yenesew A , Midiwo JO , Waterman PG.Rotenoids ,
isoflavones and chalcones from the stem bark of Mil-
lettia usarmensis subspecies usaramensis[ J] .Phyto-
chemistry , 1998 , 47(2):295-300.
[ 6] 　Antonios SM , Vassilio PP , Eugenios K.Phenolic con-
stituents from Onosma heterophylla[ J] .J Nat P rod ,
1993 , 56(6):949-952.
[ 7] 　 Jorgensen JH , Turnidge JD , Washing ton JA , et al.
Manual of Clinical M icrobiology[ M] .7th Edn.Wash-
ington DC:American Society fo r M icrobiology , 1999.
1526-1543.
滑桃树种壳化学成分的鉴定
赵沛基 ,珠 娜 ,沈月毛
(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)
摘　要:目的 研究滑桃树种壳中的化学成分 。方法 通过理化性质和光谱数据的分析鉴定了 5 个化合物的结构。结果与
结论 从滑桃树(Trew ia nudif lora L.)种壳中分离到 5个化合物 。分别鉴定为:2 , 3-二氢-3 , 6 , 7-三羟基-1-苯丙吡喃-4-酮
(1)、α, 2′, 4 , 4′-tetrahydroxydidrochalaone(2)、isoliquiritigenin(3)、3 , 4-二羟基桂皮醛(4)和 β-谷甾醇(5), 其中化合物 1 是
新化合物。化合物 3 具有一定的抗细菌活性。
关键词:药物化学;分离;鉴定;色谱分析;滑桃;2 , 3-二氢-3 , 6 , 7-三羟基-1-苯丙吡喃-4-酮
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—290— 中 国 药 物 化 学 杂 志 14卷
287
Identification of chemical constituents
of the seed crusts from Trewia nudi-
f lora L.
ZHAO Pei-ji , ZHU Na , SHEN Yue-
mao
Five compounds were obtained from the seed crusts of Trewia
nudi f lora and determined to be 2 ,3-dihydro-3 , 6 ,7-t rihydroxy-1-
H-benzo [ b ] pyran-4-one (1), α, 2′, 4 , 4′-tetrahydroxy-
didrochalaone (2), isoliquiri tigenin (3), 3-(3 , 4-dihydrox-
yphenyl)-prop-2-en-1-ol(4), β-sitosterol(5).Among those , com-
pound 1 was determined to be a new compound , named nudiflone.
Compound 3 show ed antibacterial activity.
291
Isolation , identification of the chemi-
cal constituents from Smilax glabra
Roxb.
YUAN Jiu-zhi , WU Li-jun ,
CHEN Ying-jie , LI Wei , Kazuo
Koike ,Tamotsu Nikaido Five compounds were isolated f rom the rhizome of Smilax glabra
Roxb.by column chromatography on silica gel , Diaion HP-20 ,
ODS and HPLC.Their structures w ere elucidated as n-butyl-β-D-
fructopy ranoside , n-butyl-α-D-f ructofuranoside , n-butyl-β-D-
fructofuranoside , 5-hydro xymethy lfurfural and nicotinamide re-
spectively on the basis of spect roscopic evidence.
294
Isolation , identification of the chemi-
cal constituents from Bauhinia varie-
gata L.
ZHAO Yan-yan , CUI Cheng-bin , CAI
Bing ,SUN Qi-shi
Seven compounds and a mixture w ere obtained and identified as
friedelin(1), 24(R)-9 ,19-cyclolanost-3-one-24 , 25-diol(2)and
24(S)-9 , 19-cyclolanost-3-one-24 , 25-diol (3), stigmast-3-one
(4), stigmast-4-en-3-one (5), stigmast-3β-ol-6-one (6), stigmast-
5-en-3β-ol-7-one (7), β-sitosterel(8), physicion(9).
298
Studies on the synthetic process of
darbufelone mesilate , a new non-
steroidal anti-inflammatory drug
QU Hong-qin ,ZHAO Dong-mei ,
CHENG M ao-sheng Starting from 2 , 6-di-tert-butyl-4-methyl phenol , darbufelone mesilate
can be obtained through three steps of oxidation , condensation and salt
formation.The total yield w as 58.1%.
—5—
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