全 文 ：· 334 · 药学学报 Acta Pharmaceutica Sinica 2010, 45 (3): 334−337



One new galloyl glycoside from fresh leaves of Psidium guajava L.
SHU Ji-cheng1, 2, CHOU Gui-xin1, 2*, WANG Zheng-tao1, 2*
(1. Institute of Chinese Materia Medica of Shanghai University of Traditional Chinese Medicine, The MOE Key Laboratory for
Standardization of Chinese Medicines and SATCM, Key Laboratory for New Resources and Quality Evaluation of
Chinese Medicines, The Shanghai Key Laboratory for Compound Chinese Medicines, Shanghai 201203, China;
2. Shanghai R＆D Center for Standardization of Chinese Medicines, Shanghai 201203, China)
Abstract: To investigate the chemical constituents of Psidium Guajava L, the EtOH/H2O extract of the fresh
leaves was subjected to various chromatography. Five constituents with galloyl moiety were isolated and
elucidated as 1-O-(1, 2-propanediol)-6-O-galloyl-β-D-glucopyranoside (1), gallic acid (2), ellagic acid (3), ellagic
acid-4-O-β-D-glucopyranoside (4) and quercetin-3-O-(6-galloyl) β-D-galactopyranoside (5) by spectroscopic
methods, including 2D NMR and HR-ESI-MS spectrometry as well as by comparison with published data.
Compounds 4 and 5 were obtained from P. guajava for the first time, and compound 1 is a new polyhydroxyl
compound.
Key words: Psidium guajava; galloyl glycoside; ellagic acid
CLC number: R284.1 Document code: A Article ID: 0513-4870 (2010) 03-0334-04
番石榴叶中一个新的没食子酰苷类成分
舒积成 1, 2, 侴桂新 1, 2*, 王峥涛 1, 2*
(1. 上海中医药大学中药研究所, 中药标准化教育部重点实验室, 中药新资源与质量标准综合评价国家中医药管理局重点
研究室, 上海市复方中药重点实验室, 上海 201203; 2. 上海中药标准化研究中心, 上海 201203)

摘要: 为了研究番石榴叶 Psidium guajava L.的化学成分, 用各种柱色谱方法从其乙醇水提取物中分离得到 5
个具有没食子酰结构的酚酸类化合物, 并采用光谱、质谱及文献对照等方法鉴定其结构, 分别为 1-O-(6-O-没食
子酰基-β-D-葡萄糖)-1,2-丙二醇 (1)、没食子酸 (2)、鞣花酸 (3)、鞣花酸-4-O-β-D-葡萄糖 (4)、槲皮素-3-O-(6-
没食子酰基) β-D-半乳糖 (5)。化合物 4 与 5 为首次在该植物中分离得到, 化合物 1 为一新的酚酸类化合物。
关键词: 番石榴; 没食子酰苷; 鞣花酸

Psidium guajava L. is commonly known as guava,
an important food crop and medicinal plant in tropical
and subtropical countries. Pharmacological researches
have demonstrated that this plant exhibit antioxidant[1],
anti-diarrhoeal[2], antimicrobial[3] and antidiabetic[4]
activities. The phytochemical investigation of this
medicinal herb has led the isolation of triterpenes[5],

Received 2009-11-02.
Project supported by the National Natural Science Foundation of China
(u0732004/C1905).
*Corresponding author Tel: 86-21-50271706, Fax: 86-21-50271708,
E-mail: chouguixin@yahoo.com.cn and
wangzht@hotmail.com
flavonoids[6] and some phenolic compounds. It was
reported that triterpenes and flavonoids possess antibac-
terial and anti-diarrhoeal activities[2, 7]. In this study
on P. guajava, one new and four known compounds
were isolated from this plant.

Results and discussion
Compound 1 (Figure 1) was obtained as colorless
amorphous powder. The molecular formula C16H22O11
was established from the pseudomolecular ion peak at
m/z 389.106 5 [M−H]− (calcd. 389.108 4) in HR-ESI-MS.
The IR spectrum indicated the presence of hydroxyl
DOI:10.16438/j.0513-4870.2010.03.009
SHU Ji-cheng, et al: One new galloyl glycoside from fresh leaves of Psidium Guajava L. · 335 ·

(3 414 cm−1), carbonyl (1 662 cm−1) and aromatic (1 609
cm−1) group, and 1 was found to possess a characteristic
UV spectral maximum (275 nm) in methanol which
suggested that it has galloyl ester-like characteristics[8].
A glucosyl moiety was recognized from the
following information: 1H NMR (Table 1) signals at
δ 4.22 (d, J = 7.8 Hz), δ 4.44 (1H, dd, J = 5.7, 11.9 Hz),
and 4.30 (1H, dd, J = 5.7, 11.9 Hz), and the corresponding
13C NMR signals at 103.5, 63.3; 1H NMR signals at δ
3.46, 3.12 (each 1H, m), 3.32 (2H, m), and corresponding
13C NMR signals at δ 74.1 (C-5), 73.8 (C-2), 70.4 (C-4)
and 76.3 (C-3) from HSQC experiment, and it suggested
1 possesses a β-D-glucopyranoside on the basis of the
characteristic J1, 2 coupling constant of its anomeric
proton (J = 7.8 Hz) and typical 1H and 13C NMR
shifts[9].
The 1H and 13C NMR spectra (Table 1) of 1
were close to those of 6-O-gallate of methyl β-D-
glucopyranoside[10], the main difference between 1 and
6-O-gallate was the propanediol functionality for 1,
instead of the methyl signal in 6-O-gallate. The
1H NMR signals for six protons at δ 3.67 (1H, dd, J =
10.2, 3.3 Hz), 3.25 (1H, dd, J = 10.2, 2.0 Hz), 3.84 (1H,
m), and 0.99 (3H, d, J = 6.4 Hz), and the corresponding
13C NMR signals at δ 75.3 (C-1), 66.3 (C-2) and 17.7

Table 1 The NMR spectroscopic data for compound 1
Position 1Ha 13Cb HMBC (H-C)
1 4.22 (d, J = 7.8 Hz) 103.5 C-1, C-3
2 3.12 (m) 73.8 C-1, C-3, C-4
3 3.32 (m) 76.3 C-1, C-5
4 3.32 (m) 70.4 C-6, C-2
5 3.46 (m) 74.1 C-3, C-4, C-6
6 4.44 (dd, J = 5.7,11.9 Hz) 63.3 C-4, C-5, C-7
4.30 (dd, J = 5.7,11.9 Hz)
1 3.67 (dd, J = 3.3,10.2 Hz) 75.3 C-1, C-2, C-3
3.25 (dd, J = 2.0,10.2 Hz)
2 3.84 (m) 66.3 C-1, C-3
3 0.99 (d, J = 6.4 Hz) 17.7 C-1, C-2
1 120.0
2 6.98 (s) 103.5 C-1, C-3, C-4,
C-6, C-7
3 145.1
4 140.2
5 145.1
6 6.98 (s) 103.5 C-1, C-2, C-4,
C-5, C-7
7 166.9
a500 MHz, MeOH-d4; chemical shifts in ppm relative to
TMS; coupling constants (J) in Hz. b125 MHz, MeOH-d4; All
assignments based on the extensive 1D and 2D NMR spectra

Figure 1 The structure of compound 1


Figure 2 The key HMBC correlations of compound 1

(C-3) suggested a 1,2-propanediol moiety[11]. The
HMBC correlations (Figure 2) of the anomeric proton
at δ 4.22 with C-3, 5, 1, and H-1 with C-1, 3, and
H-6 with C-7″ suggested that 1, 2-propanediol could
be located to C-1 and the galloyl to C-6. Thus, the
structure of 1 was established as 1-O-(1, 2-propanediol)-
6-O-galloyl-β-D-glucopyranoside, however, the absolute
configuration at C-2 is not known.

Experimental
1 General procedure and reagents
NMR spectra were obtained on Bruker AV-500 or
Bruker AV-400 and with TMS as internal reference,
using DMSO-d6 or CD3OD as solvents. Electrospray
ionisation (ESI) mass spectra were acquired on a LCQ
DECAXP mass spectrometer (Thermo Finnigan, San
Jose, CA, USA) equipped with an ion trap mass analyzer.
HR-ESI-MS were obtained on Waters UPLC Premir
Q-TOF. IR spectra were recorded on NicoletTM-380
spectrophotometer from Thermo Electron. Supercritieal
carbon dioxide fluid extraction (CO2-SFE) was
performed on HA420-40-96-EX from Nantong Huaan
Above-critical Extraction Co., Ltd., China. Melting
points were measured on Büchi-Meting-Point-B-540
apparatus and were uncorrected. Column chromatog-
raphy (CC): silica gel (200-300 mesh; Qingdao Haiyang
Chemical Co., Ltd., Qingdao, China), ODS (SepaxGP-
C18, 40−60 μm, Sepax Technologies Inc.) and Sephadex
LH-20 (GE-Healthcare Bio-Sciences AB, Uppsala,
Sweden) as packing materials. All other chemicals
were of analytical grade.
2 Plant material
Leaves of Psidium guajava were collected in
· 336 · 药学学报 Acta Pharmaceutica Sinica 2010, 45 (3): 334−337

spring in Guangzhou, Guangdong Province of China,
and identified by Professor Xiaoping Lai (Guangzhou
University of Traditional Chinese Medicine). A voucher
specimen (No. 20070504) was deposited in Shanghai
R& D Center for Standardization of Chinese Medicines.
3 Extraction and isolation
Psidium guajava leaves (10 kg) were extracted
with CO2-SFE to remove fat and volatile oil, the dregs
were extracted with 70% (v/v) aqueous methanol (80 L ×
3) at room temperature. The extracts were combined
and concentrated under reduced pressure and the
residue was suspended in water. The suspension was
fractionated successively with ethyl acetate and
n-butanol. The ethyl acetate residue (189 g) was
separated over silica gel column eluted with CH2Cl2-
MeOH (100∶0→1∶1, v/v) to yield four fractions A1→
A4, A2 (28 g) was separated over silica gel column
eluted with CH2Cl2-MeOH (20∶1, v/v) to yield 2
(205 mg) and 3 (220 mg). The n-butanol residue
(380 g) was separated over silica gel column eluted
with EtOAc-MeOH (100∶0→1∶1, v/v) to yield four
fractions B1→B4. B2 (76 g) was further separated
over silica gel column eluted with EtOAc-MeOH-H2O
(20∶2∶1, v/v) to yield 4 (50 mg) and 5 (21 mg). B3
(46 g) was separated over ODS column eluted with
MeOH- H2O (2∶8→1∶0, v/v) to yield 1 (16 mg).

Structure identification
1-O-(1,2-propanediol)-6-O-galloyl-β-D-glucopy-
ranoside (1): amorphous powder (MeOH). HR-ESI-MS:
m/z 389.106 5 [M−H]− (calcd. 389.108 4). IR (cm−1):
3 414, 1 662, 1 609, 1 562, 1 495, 1 446, 1 310, 1 198.
UV: 275 nm. 1H NMR and 13C NMR see Table 1.
Gallic acid (2): white needles (MeOH), mp 251−
252 ℃. ESI-MS: m/z 171 [M+H]+. 1H NMR (CD3OD)
δH: 7.04 (2H, s, H-2, 6). Its 1H NMR data are consistent
with those reported[12].
Ellagic acid (3): colorless amorphous (MeOH),
mp 360−361 ℃. IR (cm−1): 3 278, 1 724, 1 612, 1 578,
1 488, 1 440, 1 360, 1 286, 1 215. ESI-MS: m/z 301
[M−H]−, 603 [2M−H]−. 1H NMR (DMSO-d6) δH: 7.46
(2H, s, H-5, 5); 13C NMR (DMSO-d6) δC: 159.1 (C-7,
7), 148.1 (C-4, 4), 139.5 (C-2, 2), 136.4 (C-3, 3),
112.3 (C-6, 6), 110.2 (C-5, 5), 107.7 (C-1,1). The
1H and 13C NMR data are in accordance with those
reported[13].
Ellagic acid-4-O-β-D-glucopyranoside (4): white
amorphous (MeOH). ESI-MS: m/z 463 [M−H]−.
1H NMR (DMSO-d6) δH: 7.69, 7.48 (each 1H, s, H-5,
5), 4.89 (1H, d, J = 7.5 Hz, glucose H-1), 3.24−3.83
(glc H-2-H-6); 13C NMR (DMSO-d6) δc: 159.3 (C-7, 7),
149.2 (C-4), 147.5 (C-4), 141.1 (C-2), 140.0 (C-3),
137.2 (C-2), 136.4 (C-3), 115.2 (C-1), 112.2 (C-5),
111.9 (C-5), 110.8 (C-6), 108.7 (C-6), 108.2 (C-1),
102.7 (C-1), 77.8 (C-5), 76.0 (C-3), 73.7 (C-2), 70.0
(C-4), 61.0 (C-6). The 1H and 13C NMR data are in
agreement with those reported[14, 15].
Quercetin-3-O-(6-galloyl) β-D-galactopyranoside
(5): yellow amorphous (MeOH). ESI-MS: m/z 615
[M−H]−. 1H NMR (DMSO-d6) δH: 7.72 (1H, dd, J =
8.5, 2.2 Hz, H-5), 7.48 (1H, d, J = 2.2 Hz, H-2), 6.88
(2H, s, H-2, 6), 6.80 (1H, d, J = 8.5 Hz, H-6), 6.39
(1H, d, J = 2.0 Hz, H-8), 6.18 (1H, d, J = 2.0 Hz, H-6),
5.20 (1H, d, J = 7.7 Hz, H-1), 4.16 (1H, dd, J = 10.7,
7.6 Hz, H-6b), 4.06 (1H, dd, J = 10.7, 5.9 Hz, H-6a),
3.72−3.74 (2H, m, H-2, 4), 3.60 (1H, t, J = 8.0 Hz,
H-5), 3.46 (1H, dd, J = 9.6, 3.0 Hz, H-3). 13C NMR
(DMSO-d6) δc: 177.3 (C-4), 165.4 (C-7), 164.1 (C-7),
161.1 (C-5), 156.4 (C-2), 156.2 (C-9), 148.1 (C-4),
144.4 (C-3, 5), 143.8 (C-3), 138.4 (C-4), 133.5
(C-3), 121.2 (C-6), 121.0 (C-1), 119.0 (C-1), 115.9
(C-2), 114.0 (C-5), 108.5 (C-2, 6), 103.8 (C-1, 10),
98.6 (C-6), 93.5 (C-8), 72.8 (C-3), 72.3 (C-5), 71.0
(C-2), 67.9 (C-4), 62.0 (C-6). The 1H and 13C NMR
data are resemble closely to those reported[16].
References
[1] Thaipong K, Boonprakob U, Cisneros-Zevallos L, et al.
Hydrophilic and lipophilic antioxidant activities of guava fruits
[J]. Southeast Asian J Trop Med Public Health, 2005, 36:
254−257.
[2] Zhang WJ, Chen BT, Wang CY, et al. Mechanism of
quercetin as an antidiarrheal agent [J]. Acad J First Med Coll
PLA (第一军医大学学报), 2003, 23: 1029−1031.
[3] Chah KF, Eze CA, Emuelosi CE, et al. Antibacterial and
wound healing properties of methanolic extracts of some
Nigerian medicinal plants [J]. J Ethnopharmacol, 2006, 104:
164−167.
[4] Mukhtar HM, Ansari SH, Bhat ZA, et al. Antidiabetic activity
of an ethanol extract obtained from the stem bark of Psidium
guajava (Myrtaceae) [J]. Pharmazie, 2006, 61: 725−727.
[5] Begum S, Hassan SI, Siddiqui BS. Two new triterpenoids
from the fresh leaves of Psidium guajava [J]. Planta Med,
2002, 68: 1149−1152.
[6] Arima H, Danno G. Isolation of antimicrobial compounds
from guava (Psidium guajava L.) [J]. Biosci Biotechnol
SHU Ji-cheng, et al: One new galloyl glycoside from fresh leaves of Psidium Guajava L. · 337 ·

Biochem, 2002, 66: 1727−1730.
[7] Prabu GR, Gnanamani A, Sadulla S. Guaijaverin a plant
flavonoid as potential antiplaque agent against Streptococcus
mutans [J]. J Appl Microbiol, 2006, 101: 487−495.
[8] Abou-Zaid MM, Nozzolillo C. 1-O-galloyl-α-L-rhamnose
from Acer rubrum [J]. Phytochemistry, 1999, 52: 1629−1631.
[9] Miller RE, Stewart M, Capon RJ, et al. A galloylated
cyanogenic glycoside from the Australian endemic rainforest
tree Elaeocarpus sericopetalus (Elaeocarpaceae) [J]. Phyto-
chemistry, 2006, 67: 1365−1371.
[10] Tanaka T, Nonaka GI, Nishioka I. Tannins and related
compounds. XVI. Isolation and characterization of six
methyl glucoside gallates and a gallic acid glucoside gallate
from Sanguisorba officinalis L. [J]. Chem Pharm Bull, 1984,
32: 117−121.
[11] Balboul BAAA, Ahmed AA, Otsuka H, et al. 4-Hydroxy-
phenylpropan-7,8-diols and derivatives from Narvalina
domingensis [J]. Phytochemistry, 1996, 42: 1191−1193.
[12] Wang SM, Liu ZQ, Liu SY, et al. Studies on the anti-free
radical compounds in Tuocha (Camellia sinensis var. assamica)
[J]. Nat Prod Res Dev (天然产物研究与开发), 2005, 17:
131−137.
[13] Zhu HX, Tang YP, Gong ZN, et al. Chemical constituents of
Discocleidion rufescens (III) [J]. Chin Trad Herb Drugs (中
草药), 2008, 39: 1613−1617.
[14] Yoshida T, Amakura Y, Liu YZ, et al. Tannins and related
polyphenols of euphorbiaceous plants. XI. Three new
hydrolysable tannins and a polyphenol glucoside from
Euphorbia humifusa [J]. Chem Pharm Bull, 1994, 42: 1803−
1807.
[15] Liu D, Jiu JH, Yang JS. Studies on chemical constituents
from Tetrastigma hypoglaucum [J]. Chin Tradit Herb Drugs
(中草药), 2003, 34: 4−6.
[16] Kadota S, Takamori Y, Nyein K, et al. Constituents of
the leaves of Woodfordia fruiticosa KURZ. I. Isolation,
structure, and proton and carbon-13 nuclear magnetic resonance
signal assignments of woodfruticosin (Woodfordin C), an
inhibitor of deoxyribonucleic acid topoisomerase II [J]. Chem
Pharm Bull, 1990, 38: 2687−2697.









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中国药学会-石药集团青年药剂学奖是中国药学会与石药集团共同设立的青年药剂学奖, 旨在奖励中
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