Fitoterapia 81 (2010) 532535

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Fitoterapia
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f i t o t e

Two new benzophenone glycosides from the fruit of Psidium guajava L.

Jicheng Shu, Guixin Chou , Zhengtao Wang
a
The MOE Key Laboratory for Standardization of Chinese Medicines, Institute of Chinese Materia Medica of Shanghai University of Traditional Chinese Medicine, Cai Lun
Road 1200, Zhangjiang, Shanghai, 201203, China
b
SATCM Key Laboratory for New Resources and Quality Evaluation of Chinese Medicines, Institute of Chinese Materia Medica of Shanghai University of Traditional
Chinese Medicine, Cai Lun Road 1200, Zhangjiang, Shanghai, 201203, China
c
Shanghai R&D Center for Standardization of Chinese Medicines, Shanghai 201203, China

a r t i c l e

i n f o

Article history:
Received 11 November 2009
Accepted in revised form 30 December 2009
Available online 18 January 2010
Keywords:
Psidium guajava L.
Benzophenone glycosides
Spectroscopic methods

a b s t r a c t
The ripe edible fruits of Psidium guajava L. was phytochemically investigated, three benzophenone
glycosides, 2, 6-dihydroxy-3, 5-dimethyl-4-O--D-glucopyranosyl-benzophenone (1), 2, 6dihydroxy-3-methyl-4-O-(6-O-galloyl--D-glucopyranosyl)-benzophenone (2), 2, 6dihydroxy-3, 5-dimethyl-4-O-(6-O-galloyl--D-glucopyranosyl)-benzophenone (3) were
isolated by means of chromatography, and their structures were elucidated on the basis of mass
spectrometry, 1H NMR, 13C NMR, HSQC and HMBC data. Compounds 1 and 2 were new
benzophenone glycosides, and here we report the complete spectroscopic assignments for 3.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Psidium guajava L. (Myrtaceae) is commonly known as
Guava, an important food crop and medicinal plant in tropical
and subtropical countries. Different parts of the plant are
reported for the treatment of skin ailments such as antidiarrhoeic, stomach ache, wounds, cold, cough and fever. The
ower buds are used as a tonic in diseases of digestive
function [1]. The decoction of leaves and shoots is viewed as a
febrifuge and spasmolytic [2]. The bark is prescribed as an
astringent and as an antidiarrhoeatic in children [3]. The
bark and leaves are reported for skin ailments [4]. The fruit
is a tonic and laxative and is good in bleeding gums [5].

Phytochemical studies have resulted in the isolation and

identication of various terpenoids, avonoids and tannins
[68], and a recent review on the traditional uses, phytochemistry and pharmacology of the specie had reported in
detail [9], but some doctors often use the plant for curing
u in Lingnan of China. During the search for anti-uenza
activity compounds from medicinal plants in Linnan of China,
we investigated the fruit of P. guajava led to the isolation
of two new and one known benzophenone glycoisdes, 2,
6-dihydroxy-3, 5-dimethyl-4-O--D-glucopyranosyl-benzophenone (1), 2, 6-dihydroxy-3-methyl-4-O-(6-O-galloyl--Dglucopyranosyl)-benzophenone (2), 2, 6-dihydroxy-3, 5-dimethyl-4-O-(6-O-galloyl--D-glucopyranosyl)-benzophenone
(3).
2. Materials and methods

Corresponding authors. The MOE Key Laboratory for Standardization of

Chinese Medicines and SATCM Key Laboratory for New Resources and
Quality Evaluation of Chinese Medicines, Institute of Chinese Materia Medica
of Shanghai University of Traditional Chinese Medicine, Cai Lun Road 1200,
Zhangjiang, Shanghai, 201203, China. Tel.: +86 21 50271706; fax: +86 21
51322519.
E-mail addresses: chouguixi@yahoo.com.cn (G. Chou),
wangzht@hotmail.com (Z. Wang).
0367-326X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.tote.2010.01.014

2.1. Plant materials

Fruits of P. guajava, collected in Guangzhou city Guangdong province China, and was identied by Prof. Lai Xiaoping
of Guangzhou Traditional Chinese Medicine University. A
voucher specimen (NO. 20080507) was deposited in Shanghai R&D Center for Standardization of Chinese Medicines.

J. Shu et al. / Fitoterapia 81 (2010) 532535

533

was suspended in water, extracted successively with ethyl

acetate and n-butanol. Parts of the dried ethyl acetate extract
(189 g) were applied to cc (silica gel, CHCl2/MeOH, 100:0 to
1:1) to afford 5 fractions. Fraction 4 (23 g) was further
subjected to cc (silica gel, EtOAc/MeOH, 10:1; then Sephadex
LH-20 (MeOH)) to afford 1 (22 mg, 0.00022%), 2 (10 mg,
0.0001%), 3 (15 mg, 0.00015%).
2, 6-dihydroxy-3, 5-dimethyl-4-O--D-glucopyranosylbenzophenone (1), yellow powder (MeOH), mp 162-164 C.
[]D25 -78.1 (c 0.016, MeOH); IR (KBr): 3408 (OH), 2929
(CH), 1606 (C O), 1572 (C C), 1328, 1263, 906, 659. HRESI-MS
m/z: 419.1355 (calcd. 419.1342 for C21H24O9H). 1H NMR and
13
C NMR data see Table 1.
2, 6-dihydroxy-3-methyl-4-O-(6-O-galloyl--D-glucopyranosyl)-benzophenone (2), yellow powder (MeOH), mp
187-189 C. []D25 -92.9 (c 0.035, MeOH). IR (KBr): 3403
(OH), 2922 (CH), 1700 (C O), 1616 (C O), 1448 (C C), 1328,
1231, 1069, 1035, 766. HRESI-MS m/z: 557.1290 (calcd.
557.1295 for C27H26O13-H). 1H NMR and 13C NMR data see
Table 1.
2, 6-dihydroxy-3, 5-dimethyl-4-O-(6-O-galloyl--D-glucopyranosyl)-benzophenone (3): yellow powder (MeOH),
mp 195196 C. ESI-MS m/z: 573 [M+H]+. HRESI-MS m/z:
571.1436 (calcd. 571.1452 for C28H28O13-H). 1H NMR and 13C
NMR data see Table 1 (Fig. 1).

2.2. General procedure and regents

1

H (500 MHz), 13C (125 MHz), and 2D NMR spectra were

obtained on Bruker AV-500 and with TMS as internal
reference, used deuterated dimethyl sulfoxide (DMSO-d6)
as solvents. Electrospray ionisation (ESI) mass spectra were
acquired in the positive ion mode on a LCQ DECAXP
instrument (Thermo Finnigan, San Jose, CA, USA) equipped
with an ion trap mass analyzer. HR-ESI-MS were obtained in
the negative ion mode on Waters UPLC Premir Q-TOF. IR
spectra were obtained on NicoletTM-380 spectrometer from
Thermo Electron; in cm 1. Supercritical carbon dioxide uid
extraction (CO2-SFE) was performed on HA420-40-96-EX
from Nantong Huaan above-critical extraction CO., Ltd. China.
Melting points were measured by Bchi-Meting-Point-B-540
apparatus, uncorrected. Optical rotations were acquired on
Krss-P800-T polarimeter. TLC plates were HSGF254 SiO2
from Yantai Jiangyou Silica Gel Development Co., Ltd., China.
Column chromatography (CC) silica gel (SiO2; 200300
mesh; Qingdao Haiyang Chemical Co., Ltd., Qingdao, China),
Sephadex LH-20 (GE-Healthcare Bio-Sciences AB, Uppsala,
Sweden) as packing materials. All other chemicals were of
analytical reagent grade.
2.3. Extraction and isolation
The dried fruits of P. guajava (10 kg) were defatted by
CO2-SFE and extracted with 70% (v/v) aqueous ethanol
(80 L 3) at room temperature. The 70% EtOH extract was
concentrated under reduced pressure to give a residue, which

3. Results and discussion

Compound 1 was obtained as yellow powder. It gave a
positive result for the ferric chloride reaction, revealing its

Table 1
1
H, 13C NMR (DMSO-d6) data of compound 1, 2 and 3 (500 MHz and 125 MHz, J in Hz, in ppm).
C

1
2
3
4
5
6
7
8
9
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
7

1 (DMSO-d6)

2 (DMSO-d6)

3 (DMSO-d6)

113.0
152.1
111.0
156.2
111.0
152.1
197.0
9.9
9.9
138.9
128.7
128.2
132.4
128.2
128.7
104.2
74.1
76.4
69.9
76.8
61.1

2.10 (s)
2.10 (s)

7.69 (dd, J = 1.3, 7.0)

7.48 (like t, J = 7.5, 7.7)
7.58 (like t, J = 7.3)
7.48 (like t, J = 7.5, 7.7)
7.69 (dd, J = 1.3, 7.3)
4.56 (d, 7.6)
3.29 (m)
3.24 (m)
3.15 (m)
3.06 (m)
3.63 (dd, 1.9, 11.6)
3.45(dd, 5.6, 11.6)

108.3
156.7
104.7
159.2
94.8
156.0
197.2
8.1

139.6
128.5
128.0
132.0
128.0
128.5
101.1
73.2
76.3
69.0
73.8
62.6

112.9
156.6
111.9
159.9
111.9
156.6
201.5
10.2
10.2
142.0
130.2
129.3
133.2
129.3
130.2
105.8
75.8
78.1
71.8
76.1
64.6

2.15
2.15

7.59
7.35
7.48
7.35
7.59
4.74
3.58
3.54
3.48
3.45
4.42
4.38

7.15

7.15

119.3
108.6
145.5
138.5
145.5
108.6
165.8

6.20 (s)

1.97 (s)

7.68 (dd, J = 1.0, 7.2)

7.45 (like t, J = 7.4, 7.7)
7.55 (like t, J = 7.3)
7.45 (like t, J = 7.4, 7.7)
7.68 (dd, J = 1.0, 7.2)
4.85 (d, 7.3)
3.52 (m)
3.48 (m)
3.42 (m)
3.38 (m)
4.304.40 (m)

7.15 (s)

7.15 (s)

121.7
110.5
146. 7
140.1
146.7
110.5
168.6

(s)
(s)
(dd, J = 1.2, 7.0)
(like t, J = 7.6, 8.9)
(like t, J = 7.5)
(like t, J = 7.6, 8.9)
(dd, J = 1.2, 7.0)
(d, 7.6)
(m)
(m)
(m)
(m)
(dd, 2.0, 11.9 )
(dd, 4.6, 11.9)
(s)

(s)

534

J. Shu et al. / Fitoterapia 81 (2010) 532535

Fig. 1. Structures of compounds 13.

phenolic nature. The IR spectrum of 1 showed the presence of

hydroxyl groups (34083039 cm 1), conjugated carbonyl
(1606 cm 1) and aromatic (1572 cm 1) absorption bands.
The molecular formula of 1 was conrmed to be C21H24O9 by
HR-ESI-MS at m/z: 419.1355 [M-H] and 13C NMR. The 1H NMR
spectrum showed signals of two magnetic equivalent phenolic
hydroxyl ( 8.79, 2H, s), two magnetic equivalent methyl (
2.10, 6H, s) were indicative of symmetrical substitution of ring
A. The 1H NMR spectrum also contained signals for a phenyl
group at H 7.69 (2 H, dd, J2, 3 = J5, 6 = 7.0 Hz, J2, 6 = 1.3 Hz,
H-2 and H-6), H 7.58 (1 H, like t, J4,3 = J4,5 = 7.3 Hz, H-4)
and H 7.48 (2 H, like t, J = 7.5, 7.7 Hz, H-3 and H-5) for ring
B. The anomeric proton signal (H 4.56 d, J1, 2 = 7.6 Hz, H-1),
other signals in the 1H NMR spectrum at H 3.063.63 ppm
and signals in the 13C NMR spectrum corresponding to 6 sugar

carbons at C 104.2, 76.8, 76.4, 74.1, 69.9, and 61.1 from HSQC
experiment were characteristic of a -glucopyranosyl residue
[10]. In HMBC spectrum of 1 (Fig. 2), the aromatic protons of
ring B at H 7.69 (H-2 and H-6) showed cross-peaks with the
carbonyl carbon (C 197.0), methyl protons at H 2.10 (6H, H8 and H-9) correlated with C-2, 3, 4, 5, 6 implied that the two
methyl groups were located at C-3 and C-5, while hydroxyl
groups at H 8.79 (2H, s) showed correlations with C-1, 2, 3, 5,
6 in ring A, which suggested the two hydroxyl groups was
placed at C-2 and C-6. The anomeric proton at H 4.56
exhibited HMBC cross-peaks with a C-4 quaternary carbon at
C 159.2, therefore C-4 was identied as the linkage position of
glucoside. Based on these ndings the structure of 1 was
established as 2, 6-dihydroxyl-3, 5-dimethyl-4-O--D-glucopyranosyl-benzophenone.

Fig. 2. Signicant HMBC (H C) correlations of compounds 1 and 2.

J. Shu et al. / Fitoterapia 81 (2010) 532535

Compound 3 was shown to have molecular formulas of

C28H28O13 by HRESI-MS at m/z 571.1436 [M-H]. The 1H and
13
C NMR spectroscopic data of 3 were similar to those of 1,
except for the appearance of galloyl signals in 1H and 13C NMR
spectra data H 7.15 (2H s) and C 121.7 (1), 110.5 (2, 6),
146. 7 (3, 5), 140.1 (4), 168.6 (7). The location of the
galloyl group at O-6 of the glucose residue was determined
by comparison of the 1H and 13C NMR spectra of 3 with those
of 1, compound 3 showed a remarkable downeld shift: 0.79
and 0.93 ppm of H-6, and 3.5 ppm of C-6, respectively. So
compound 3 was identied as 2,6-dihydroxy-3,5-dimethyl-4O-(6-O-galloyl--D-glucopyranosyl)-benzophenone, it was
isolated previously from the leaves of the plant [11].
1
H- and 13C NMR spectra of compound 2 were very similar
to those of 3, except for one aromatic proton at H 6.20 (1H, s)
of 3 replacing one methyl at H 1.97 (3H, s) signal of 3 on C-5,
the molecular formula of 2 was conrmed to be C27H26O13 by
HRESI-MS m/z: 557.1290 [M-H]. A combination of NMR and
mass spectral data suggested to us that 2 was an analog of 3.
In HMBC spectra, the aromatic proton at H 6.20 (1H, s, H-5)
showed correlations with C-1, 3, 4, 6, and methyl protons at
H 1.97 (3H, s, H-8) showed interactions with C-2, 3, 4, which
suggested that the methyl group was located at C-3, the
correlation of a hydroxyl group at H 10.05 (1H, s) with C-1, 2,
3 implied that the hydroxyl group was placed at C-2, while
the long-range correlation between another hydroxyl group
at H 9.24 (1H, s) and C-1, 5, 6 suggested that the OH group
was located at C-6. The anomeric proton at H 4.85 (d,
J = 7.3 Hz) showed correlations with C-4, the two protons of
C-6 of sugar at H 4.30 4.40 (m) showed interactions with C7 at C 165.8, these were identied that the glucose group
and the galloyl group were attached at C-4 and C-6,
separately. Based on these ndings the structure of com-

535

pound 2 can be elucidated as 2, 6-dihydroxy-3-methyl-4-O(6-O-galloyl--D-glucopyranosyl)-benzophenone.

Acknowledgement
This research was supported by the National Natural
Science Foundation (Grant No. u0732004/C1905).

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