全 文 ：Jou rnal of Ch inese Pharm aceutica l Sc iences 2006, 15(1):21-23 21　
Chem ical Constituents from Piper wallichii
ZHAO Yun and RUAN Jin-lan*
(College of Pharmacy, TongjiM edica lCenter, Huazhong University of S cience and Technology, Wuhan 430030 , China)
Received date:2005-08-21.
* Correspond ing:Te l86-27-83692892,
E-m ai l jin lan5952@ hotm ai.l com
Abstract:Ami 　To investiga te the chem ical constituents o fP iperwallich ii. Methods　Five com-
pounds we re isola ted by silica ge l co lumn chrom atog raphy and Sephadex LH-20 ge l co lumn chromatog ra-
phy, and the structures of compounds we re identified by spectral analy sis. Result　Five compounds
w ere identified as piperlongum inine (trans, trans)(1), 4-hydroxy-3, 5-dime thoxy-benzoic acid (2), gal-
g rav in (3), β-sitostero l(4), and daucosterol(5). Conclusion　Five compounds were iso lated from P iper
wallichii for the first time, and compounds 1 -3we re iso lated from this genus for the first time.
Key words:P iperwallichii;piperlongum in ine;4-hydroxy-3, 5-d imethoxy-benzo ic acid;ga lg ravin
CLC number:R284. 1;R284. 2　Document code:A 　Article ID:1003-1057(2006)1-021-03
In troduction
P iperwallichii is a perennial herb o f the genus Pip-
er, which belongs to the fam ily P ipe raceae. Its aerial part
is used as an e ffective fo lk medicine to treat be riberoid
disease, allev iate pain, dredge meridian passage, and
improve sexual function a tYangzi River drainage area
[ 1]
.
In our prev ious work, we reported three aristo lochialac-
tams extracted from it
[ 2]
. Further investigation o f its pe-
troleum ethe r fraction and ethy l acetate fraction has led to
the isolation of five compounds identified as piperlongu-
m inine ( trans, trans) (1), 4-hydroxy-3, 5-dimethoxy-
benzo ic acid (2), ga lg rav in (3), β-sitostero l(4), and
daucosterol(5). A ll compounds were iso la ted from this
plant for the first time. And compounds 1 -3were isola-
ted from this genus for the first time.
Resu lts and D iscussion
The ethano lic extract from the plan t w as m ixed
w ith k iese lguhr, and extrac ted w ith petro leum e ther,
ethy l aceta te, and methano l, successively. The pe tro-
leum e ther frac tion and e thy l aceta te fraction w ere sub-
jec ted to repea ted co lumn chromatography to afford five
compounds.
C ompound 1 was obta ined as w hite needles. The
molecula r formula C16H19O 3N was deduced from E I-MS
m /z 273 [M ] + and 13 C NMR spectral data. The ion
peak atm /z 273 , 230, 216, 201, and 173 in theM S
spectrum suggested the presence o f-CONHCH2CHM e2
moie ty. The
13
C and
1
H NMR spec tral data show ed the
characteristic signals o f methy lenedioxy (1H δ6. 06,
13
C δ101. 9). In addition, the 13C NMR spectral data
revealed the presence of an arom atic ring (δ148. 8,
148. 7, 140. 2, 131. 7, 138. 4, 125. 7), and four
methy lenes (δ125. 1, 123. 0, 108. 8, 106. 0). F rom
the above data, compound 1 was evidenced as an
aroma tic compound w ith an am ide and a methy lened-
ioxy g roup. A ll the spectra data of 1 a re in ag reemen t
w ith those o f piperlongum inine (trans, trans ) repor-
ted
[ 3]
.
C ompound 2 was obta ined as w hite needles. The
molecula r fo rmu laC9H 10O 5 was deduced by EI-MSm /z
198 [M ] +, 13 C and 1H NMR data. The 13 C NMR
signal at δ56. 0 and the 1H NMR signal at δ3. 79
show ed the presence of tw o me thoxy l g roups. In addi-
tion, the 13 C NMR data ind ica ted the presence of an
aroma tic ring (δ147. 4, 147. 4, 140. 0, 120. 3, 106. 8,
106. 8) and a carbox lic carbon (δ167. 2). And the
carbox lic carbon w as attached to the a roma tic ring. A ll
the spectra l data of 2 are in agreement w ith those o f
4-hyd roxy-3, 5-dimethoxy-benzo ic acid reported[ 4] .
C ompound 3 was obta ined as w hite needles. The
22　 Journa l o f Chine se Pharm aceu tical Sciences 2006, 15(1):21-23
mo lecu lar fo rmu la C22H28O 5 was a lso deduced from E I-
MSm /z 372[M ] +, 13 C and 1H NMR data. The 1H
NMR da ta showed the presence o f fou rme thoxy l g roups
(δ3. 81, 3. 79), and two methy l g roups (δ1. 01).
13
C NMR data a lso show ed fou r methoxy l g roups
(δ55. 7, 55. 8). The M S signa ls atm /z 51, 77, 91
indica ted the presence an aromatic ring. The HSQC
data show ed co rrelations between C-7 (δ87. 5) and
H-7 (δ4. 35), indicating that C-7 is a ttached to -O or
-OH;there a re a lso co rre lations be tw een C-8 (δ45. 1)
and H-8 (δ2. 27). And there is no -CH2-in this com-
pound deducing from DEPT. Thus compound 3 was
identified as ga lg ravin.
Experimen tal
Ggenera l
M elting point w as determ ined on Tek tronix X-5
me lting point de tec to r.
1
H NMR and
13
C NMR spectra
w ere recorded on a Bruke r-400 (1H NMR 400MHz,
13
C NMR 100MHz) instrumen.t M S spectra w ere taken
on a ZAB-HF-3 spectrometer. Silica ge l (200 - 300,
300 -400mesh, Q ingdao Ocean Chem ical Factory), and
Sephadex LH-20 (Pharmacia) we re used fo r chromato-
graphic separations.
P lantma terial
The ae ria l part of P iper wallich ii was pu rchased
from Wufeng County, Hube i Province, and identified
by assoc iate chief pha rmac ist Zhou Zu-hai, Institute of
Drug Con trol of Wufeng County. Voucher specim ens
w ere deposited in the he rbarium of C ollege of pharma-
cy, Tong ji med ica l Cen ter, Huazhong Unive rsity of
Science and Technology.
Extraction and isolation
Dried and powdered aerial part of P iper wallich ii
(17. 2 kg)was ex tracted w ith 95% E tOH once, then
w ith 70% E tOH tw ice. A fte r the solventw as evapora t-
ed under reduced pressure, the residue (1 127. 5 g)
was m ixed w ith kieselguhr, and extrac ted w ith petro le-
um e ther, e thyl aceta te, and methano l, successive ly.
The pe troleum e ther ex tract w as subjected to silica gel
co lumn ch roma tography w ith petro leum e ther-ace tone
m ix ture increasing polarities as an e luen t to y ield com-
pound 3 (20.3 mg), and compound 4 (70.3 mg).
The e thy l ace tate ex tractw as sub jected to silica ge l co l-
umn chroma tography, using increasing po la rities o f
chlorofo rm-methano lm ix ture as so lvent system to g ive
compound 1 (33.2 mg), 2 (31.3 mg), and 5
(100.5mg).
F igure 1　Struc tures of com pounds 1 - 3　　
Structure iden tification
Compound 1　White need les, mp 136.8 -
138.4 ℃, 1H NMR (DMSO-d6):δ7. 29 (1H , m , 3-
H), 7. 11 (1H , d, J =1. 6 Hz, 2′-H), 6. 98 (1H ,
dd, J =1. 7, 8. 0 H z, 6′-H), 6. 86 (3H , m , 4, 5,
5′-H), 6.18 (1H , d, J =14. 8 Hz, 2-H), 6. 01
(2H , s, -OCH 2O-), 3. 09 (2H , m , -NCH2), 1. 79
(1H , m , -CHM e2), 0. 88 (6H , m , 2 ×CH3);13 C
NMR(DMSO-d6):δ166. 1 (C =O), 148. 8(C-3),
148. 7 (C-4′), 131. 7(C-1′), 101. 9(-OCH 2O-),
140. 2, 138. 4, 125. 7, 125. 1, 123. 0, 108. 8,
106. 0, 46. 9(-NHCH2 ), 28. 9 (-CHM e2), 20. 1
(CH3 ×2);EI-MS m /z:273 (M +), 230 , 216, 201,
187, 173 , 151, 143 , 135, 115, 96, 89, 65, 57, 51.
The
1
H NMR and E I-MS data of 1 are in agreementw ith
those of pipe rlongum inine (trans, trans) reported[ 3] .
Compound 2　White needles, 1H NMR (DMSO-
d6):δ7. 20 (2H , d, J = 1. 1 Hz, 2, 6-H), 3. 79
(6H , s, -OCH3 );13 C NMR (DMSO-d6 ):δ167.2
(-COOH), 147. 4 (C-3), 147. 4 (C-5), 140. 0
ZHAO Yun, et a l:Chem ical Constituen ts from P iper wa llich ii 23　
(C-4), 120. 3 (C-1), 106. 8 (C-2), 106. 8(C-6),
56. 0 (-OCH3), 56. 0 (-OCH 3);E I-MS m /z:198
(M +), 183, 168, 153 , 127, 109, 93, 77, 65. The
1
H NMR and E I-MS data of 2 are in ag reement w ith
those o f 4-hydroxy-3, 5-d imethoxy-benzoic acid[ 4] .
Compound 3　Wh ite needles, 1H NMR (ace-
tone-d6):δ7. 09 (2H , d, J =1. 93 H z, 2, 2′-H),
6.93 (2H , d , J =8. 59, 1. 92H z, 5, 5′-H), 6. 99
(2H , dd, J = 8. 59, 1. 92 H z, 6, 6′-H ), 4. 45
(2H , d, J =6. 46H z, 7, 7′-H), 2. 27 (2H , m , 8,
8′-H), 1.01 (6H , d, J = 8. 25 Hz , 9, 9′-H ) ,
3.81 (6H , s, 4 , 4′-OCH3) , 3. 79 (6H , s, 5, 5′-
CH 3);13 C NMR (ace tone -d6):δ135. 8(C-1, 1′),
110. 7(C-2, 2′), 149. 9 (C-3, 3′), 149. 3 (C-4,
4′), 112. 1(C-5, 5′), 119. 1(C-6, 6′), 87. 5(C-7,
7′), 45. 1 (C-8, 8′), 12. 7 (C-9, 9′), 55. 8
(OCH 3 ×2);55. 7 (OCH3 ×2);MS m /z:372
(M +), 206, 191, 175 , 160, 138, 115, 91, 77, 51.
The struc ture w as supported by HSQC and HMBC ex-
perimen ts. The NMR da ta are in ag reement w ith those
o f(7s, 7′s)-diveratry l-(8 r, 8′s)-dime thy ltetrahydro-
furan
[ 5]
.
Compound 4 and 5　were identified as β-sitostero l
and daucostero l, respective ly, by comparison w ith au-
thentic substances.
Refe rences
[ 1] La i XP, L iu XC. H erbalogica l study on P iper wa llichii
[ J] . J Guangzhou Univ Trad it Chin M ed, 1994, 11(2):
105-110.
[ 2] Zhao Y, Ruan JL, C ai YL. Th ree a risto lola tam s from P iper
wallichii [ J] . J Chin M ed M ater, 2005, 28 (3):
191-192.
[ 3] Sonia, WB. Am ides o f O ttonia co rcovade sis [ J] . Phy to-
chem istry, 1981, 20(6):1305-1307.
[ 4] Shogo, M S, HK, et al. A romatic g lycosides from Berchem ia
racemosa [ J]. Phytochem istry, 1987, 26(10):2811-2814.
[ 5] Yu DQ et al. Handbook of Ana ly tica lChem istry [ M ] . Bei-
jing: Chem ical and Industra l Publish ing House,
1993. 778.
石南藤化学成分研究
赵　云 , 阮金兰
(华中科技大学 同济药学院 , 湖北 武汉 430030)
摘要:目的　对石南藤 P iper wa llich ii化学成分进行研究。方法　应用硅胶 、葡聚糖凝胶等色谱技术分离纯化 , 应用波谱
技术确定化合物的结构。结果　从石南藤中分离得到了 5个化合物 , 分别为 p iperlongum inine (trans, trans) (1), 4-羟基-3, 5-
二甲氧基-苯甲酸 (2), ga lg rav in (3), β-谷甾醇 (4)以及胡萝卜苷 (5)。结论　五个化合物均为首次从石南藤中得到 , 化合物
1 ～ 3为首次从胡椒属中得到。
关键词 :石南藤;胡椒碱;4-羟基-3, 5-二甲氧基-苯甲酸;ga lg rav in