全 文 ：　　　　 　　天然产物研究与开发　 　　　　　
　　　　　　　　　　 NATURAL PRODUCT RESEARCH AND DEVELOPMENT 2005　Vol.17　No.1
　
　
　
　
　　Received July 15 , 2004;accepted October 22 , 2004
　　Foundat ion Item:This work was supported by the National Natural Sci-
ence Foundation of China(No.29972017)
　＊Corresponding author　Tel:86-931-8912408;E-mail:jiazj@lzu.edu.cn
Studies on the Flavonoid in Polygonum periginatoris Pauls
SHEN Tong1 , JIA Zhong-jian1＊ ,ZHENG Shang-zhen2
(1.National Laboratory of Applied Organic Chemistry , Institute of Organic Chemistry , Lanzhou University ,
Lanzhou 730000 , China;2.College of Chemical Engineering , Northwest Normal University , Lanzhou 730070 , China)
Abstract:A new flavonoid , 5 , 4′-dimethoxy-6 , 7-methylenedioxyflavone-3-O-β-D-apiofuranosyl(1 ※6)-β-D-glucopranoside
(Periginatorine I), was isolated from Polygonum periginatoris Pauls , along with three known flavonoids.Their structures were
determined by spectral and chemical methods.
Key words:Polygonum periginatoris;polygonaceae;Periginatorine I
逆阿落中的黄酮化合物
沈　彤1 ,贾忠建1 ,郑尚珍2＊
(1.兰州大学国家重点有机实验室 兰州大学化学化工学院 , 兰州 730000;
2.西北师范大学化学化工学院 ,兰州 730070)
摘　要:从藏药逆阿落(Polygonum periginatoris Pauls)的乙酸乙酯提取物中分离得到四个黄酮化合物 , 通过波谱分
析及化学方法鉴定了它们的结构 ,其中 5 , 4′-二甲氧基-6 , 7-二氧亚甲基黄酮-3-O-β-D-芹糖(1※6)-β-D-葡萄糖甙
(Periginatorine I)为新化合物 , 其余三个已知黄酮类化合物为首次从该植物中分离得到。
关键词:逆阿落;蓼科;Periginatorine I
中图分类号:R284.1　　　
Introduction
Polygonum periginatoris Pauls is a traditional Chinese
medicinal herb widely distributed in China.It is used for
treatment of yellow gallbladder , roundworn , pile swelling
and so on[ 1].However , little was known about its chemical
constituents.To identify the major chemical composition of
the plant ,we have obtained the roots of Perinatoris and
isolated four flavonoids from its EtOAc extracts.In this
paper ,we report for the first time the isolation and struc-
ture elucidation of a new flavonoid ,5 , 4′-dimethoxy-6 , 7-
methylenedioxyflavone-3-O-β-D-apiofuranosyl (1※6)-β-
D-glucopryanoside (periginatorine I).The structures of
three other purified compounds were determined to be 5 ,
7-dihydroxy-4′-methoxyflavone (2)[ 2] , strobopinin-7-O-β-
D-xylopyranosyl (1※3)-β-D-xylopyranoside (3)[ 3] and
isoskuranetin-7-O-β-D-neo-hesperidoside (4)[ 4] respec-
tively by comparing their spectral data with that of authen-
tic samples or reported compounds.
Fig.1　The structure of periginatorine I
Experimental
Instruments
NMR spectra were recorded on a Bruker AM-400 spec-
tromete.Mass spectra were obtained from aMAT-112mass
spectrometer.IR and UV spectra were recorded on the
Perkin-Elmer 599B and Shimadzu UV-250 spectrometer
respectively.Melting points were measured in glass capil-
lary tubes and are uncorrected.Optical rotations were de-
termined on a Perkin-Elmer M341 polarimeter.Silica gels
were manufactured by Qingdao Marine Chemical Indus-
try.Elemental analysis was carried out on 1106 elemental
analysis apparatus.
Plant material
The roots of Polygonum periginatoris Pauls were collected
4
in Tianshui county of Gansu Province , China , in August
2003.The species was identified by Professor Lian Yong-
shan and a voucher specimen(No.32194)was deposited
in the Herbarium of the Botany Department , Northwest
Normal University.
Exraction and isolation
The dried and powdered roots of the Polygonum perigina-
toris (3 kg)were extracted three times with EtOAc at
room temperature.Filtration and evaporation of the solvent
yielded the EtOAc extract (142 mg).The extracts were
combined and the mixture was separated into three frac-
tions(A , B and C)through a polyamide column by elu-
tion with increasing gradient of hexane :EtOAc (20:1-0:
1 v/v ).Fraction A was further subjected to chromatogra-
phy on silica gel(200 ～ 300 mesh)using CHCl3:EtOAc(3:1)and CHCl3:MeOH(10:1-1:1)as solvents , result-
ing in the purification of compounds 1(28 mg)and 2(24
mg).Fraction B was purified by preparative PTLC (GF254
silica gel ,CHCl3:EtOAc:CH3OH=7:3:1 , v/v)yielding
compounds 3(19 mg)and 4(15 mg).
Hydrolysis of compound 1
To 1(8 mg)were added 7%HCl and EtOH (1 mL)and
the mixture were refluxed for 1 h.Apiose and glucose were
identified by TLCwith authentic samples [ onGF254 plate ,
solvent:n-BuOH-HOAc-H2O (4:0.5:5 v/v)] as stan-
dards.
Results and Discussion
Compound 1　Yellow crystals(from CH3OH),mp.248
～ 249 ℃,[α] 29D-97(c 0.39 ,MeOH).Both HCl-Mg and
Molish tests were positive , indicating that compound 1 may
be a flavone glycoside.The UV absorption atλmax 254 ,305
and 354 nm suggested that compound 1 is a flavone[ 7] .
The IR(KBr)spectrum showed absorption bands assigned
to aromatic(1612 ,1506 cm-1), ether bond(1257 cm-1),
methylenedioxy group (930 cm-1) and β-D-pyranoside
(890 cm-1).The ion peak at m/z 637 (M +H)+ and
343 [M-132-162] + in FAB-MS spectrum along with ele-
mental analysis led to the molecular formula C29H32O16.
The 13C NMR(DEPT)spectrum (Table 1)of compound
1 clearly exhibited 29 signals(2×CH3 , 3×CH2 , 13×
CH ,10×C ,1×CO).The 1H NMR at δ4.00(3H , s)for
methoxyl group ,peri to a carbonyl function and ortho to an
oxygenated substituent[ 5] , could be assigned to 5-
OMe.Typical AA′BB′type signals at δ7.19(2H ,d , J =
9 Hz , 3′, 5′-H), δ6.80 (2H , d , J =9 Hz , 2′, 6′-H)
were derived from proton at ring C.Thus , the methoxy
group at δ3.81 (3H , s)could be located at C4′.Con-
trolled acid hydrolysis of compound 1 released glucose and
apiose ,which were identified by TLC comparison with au-
thentic samples and the appearance of the
1
H NMR signals
at δ3.17 ～ 3.90 (m , suger protons).The 1H NMR sig-
nals at 5.08(1H ,d , J =2.4 Hz)and 4.58(1H , d , J =
8.0Hz)indicated a β-configurated apiosyl and glucosyl
moieties.The MS , IR ,UV , 1H and 13C NMR spectra of the
aglycone were similar to those of authentic sample , and
13C NMR spectral data of aglycone of 1 were very similar
with aglycone of 5 , 4′-dimethoxyl-6 , 7-methylene dioxy-
flavone-3-O-β-D-xylopyranoside[ 6].
The HMBC correlation(Fig.2)betweenH-1″′(δH 5.08)
and C-6″(δC 62.8)as well as between the H-6″(δ4.45
and 4.48)and the C-1′″(δC 108.77)suggested the
linkage of apiose (1※6)-glucose.Additionally , the HM-
BC correlation between the H-1″(δH 4.58)and C-3(δC
134.86)confirmed the location of glucose at C-3.The
methlene dioxy group δ(85.85 ,2H)at C6 and C7has also
been showed.From the above spectral data , the structure
of compound 1 could be determined as 5 , 4′-dimethoxyl-
6 ,7-methylene dioxyflavone-3-O-β-D-apiofuranosyl (1※
6)-D-glucopranoside(periginatorine I).
Table 1　NMR data of compound 1(δppm , CDCl3 , TMS)＊
№ δH δC(DEPT) № δH 　　δC(DEPT)
2 147.10(C) 1″ 4.58(1H , d , 8 Hz) 　　102.10(CH)
3 134.86(C) 2″ 3.36(1H , dd, 8.0 , 9.3 Hz) 77.01(CH)
4 177.67(C) 3″ 3.98(IH , t , 9.3 Hz) 75.96(CH)
5 154.16(C) 4″ 4.01(1H , t , 9.3 Hz) 70.69(CH)
6 137.41(C) 5″ 3.76(1H , s) 76.17(CH)
7 159.36(C) 6a″ 4.45 62.80(CH2)
8 6.31(1H , s) 96.00(CH) 6b″ 4.48
9 160.80(C) 1 5.08(1H , d , 2.4 Hz) 108.77(CH)
10 101.14(C) 2 3.86(1H , d , 2.4 Hz) 77.46(CH)
1′ 122.98(C) 3 78.82(C)
2′,6′ 6.80(2H , d , 9 Hz) 127.16(CH) 4a 3.76(1H , m) 75.04(CH2)
3′,5′ 7.19(2H , d , 9 Hz) 145.54(CH) 4b 3.90(1H , m)
4′ 165.00(C) 5 3.57(2H , s) 65.89(CH2)
5-OCH3 4.00(3H , s) 59.21(CH3)
4-OCH3 3.81(3H , s) 55.59(CH3)
O-CH2-O 5.85(2H , s) 101.49(CH2)
　＊Assignments were succeeded by 1H , 1H-COSY ,HMQC and HMBC experiments
52005　Vol.17　No.1 沈　彤等:逆阿落中的黄酮化合物 　
Fig.2　Key HMBC correlations of compound 1
Compound 2 　C16H12O5 , yellow crystals (CH3OH),
mp.260 ～ 261 ℃,FABMS m/z:285(M++1).Elemen-
tal analysis (%):C , 67.6049 , H , 4.2595 (requires:C ,
67.6056 ,H , 4.2587);UV λmax(MeOH):252 , 278 , 318
nm , the IR(KBr)vmax:3441 ,1619 ,1500 ,1668 cm-1.MS ,
1
H NMR and
13
C NMR spectral data of compound 2 were
similar to those of 5 ,6-dihydroxy-4′-methoxyflavone[ 2] and
the melting point did not decrease when it was mixed with
authentic sample.Thus , compound 2was deduced to be 5 ,
7-dihydroxy-4′-methyoxyflavone.
Compound 3　C16H30O13 , yellow slice crystal(CH3OH),
mp.202 ～ 203 ℃, FABMS m/z:551 (M++1), 271
(aglycone +H+), UV λmax(MeOH):229 (sh),288 , 345
nm.IR(KBr)vmax:3429 , 3018 , 2935 , 1641 , 1613 , 1508 ,
1105 , 1079 , 981 cm-1.1H NMR (DMSO-d6):δ2.29
(3H , s , H-6), 2.76 (1H , d , J =8.07 Hz , H-3a), 3.26
(1H ,d , J =8.0 Hz ,H-3b), 4.84 (1H ,d , J =7.64 Hz ,
H-1′), 3.72 (H-2″), 3.84 (H-3″), 3.98 (H-4″), 4.11
(H-5a″), 3.50 (H-5b″), 5.28 (1H , d , J =7.1 Hz , H-
1 ),4.01 (H-2 ), 4.05 (H-3 ), 4.21 (H-4 ), 4.53
(H-5a ), 3.73 (H-5b ), 6.81 (1H , s , H-8), 12.16
(1H , s , OH-5).The above data correspond with
strobopinin 7-O-β-D- xylopyranosyl(1※3)-β-D-xylopy-
ranoside
[ 3].
Compound 4 　 C28H34O14 , white needle crystals
(CH3OH),mp.212 ～ 213 ℃,FABMS m/ z:595(M++
H),287(M+-162-146+1).IR(KBr)vmax 3530 , 2936 ,
2912 ,1648 ,1497 ,1248 ,1158 ,1052 ,833 cm-1.EIMS m/
z:286 ,285 , 179 , 153 , 134 , 124 , 91 , 73.1H NMR (CD-
Cl3)δ:5.41(1H ,m ,H-2), 3.19 (2H , d , J =8 Hz ,H-
3),3.78(3H , s ,4′-OCH3), 3.52 ～ 3.70 (10H ,m , pro-
tons of rhamnose),12.52(1H , s ,OH-5), 7.28 (2H ,d ,
J =8.4 Hz ,H-3′, 5′), 6.95(2H , d , J =8.4 Hz ,H-2′,
6′),6.12(2H , s ,6 ,8-H),5.18(1H ,m ,H-1 of glucos),
4.95(1H , d , H-1 of rhamnose), 1.12 (3H , d , CH3 of
rhamnose).Compound 4 was determined to have the
structure of isoskuranetin-7-O-β-D-neohesperidoside[ 4].
Acknowledgments　This work was supported by the Na-
tional Natural Science Foundation of China No.29972017.
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6 天然产物研究与开发　　　　　　　　　　　　　 　　　2005　Vol.17　No.1