From the leaves of Fissistigma acuminatissima growing in Vietnam, two flavonoids, catechin and isorhamnetin-3-o-rutinoside were isolated. Their structures were characterized on the basis of MS and NMR spectra data and comparison with reported data.Keywords: Annonaeae; Fissistigma acuminatissima; catechin; isorhamnetin-3-o-rutinoside

Sung, Tran Van

Thuy, Trinh Thi

Van, Nguyen Hong

Vietnam Academy of Science and Technology: Journals Online

648
Journal of Chemistry, Vol. 45 (5), P. 648 - 651, 2007 
flavonoids from Fissistigma acuminatissima 
Received 21 December 2006 
Nguyen Hong Van, Trinh Thi Thuy, Tran Van Sung 
Institute of Chemistry, Vietnamese Academy of Science and Technology 
 
summary 
From the leaves of Fissistigma acuminatissima growing in Vietnam, two flavonoids, catechin 
and isorhamnetin-3-o-rutinoside were isolated. Their structures were characterized on the    basis 
of MS and NMR spectra data and comparison with reported data.  
Keywords: Annonaeae; Fissistigma acuminatissima; catechin; isorhamnetin-3-o-rutinoside. 
I - Introduction 
The genus Fissistigma is a large tribe with 
ca.70 species in the Annonaceae family [1]. The 
decoctions of some Fissistigma species have 
been used in Southeast Asia as traditional medi-
cines for treatment of infections and enhance-
ment of blood circulation [2]. Fissistigma acu-
minatissima (Vietnamese name C¸ch th) nhän 
or L,nh c«ng l¸ nhän) is climbing shrub grow-
ing in the north Vietnam [1]. In continuation of 
our investigation on the constituents of F. acu-
minatissima we now report the isolation and 
structural elucidation of two flavonoids, cate-
chin (1) and isorhamnetin-3-o-rutinoside (isor-
hamnetin-3-O--L-rhamnopyranosyl-(16)--
D-glucopyranosid, 2). The structures of these 
compounds were determined by MS, NMR 
techniques and comparison of those spectral 
data with reported data. 
II - Experimental 
1. General  
FT-IR: Nicolet IMPACT 410. EIMS (70 
eV): MS5989B. NMR: Bruker Avance 500, 
499.84 MHz (1H-) and 125 MHz (13C-, 13C-
DEPT). TMS ( = 0.0, 1H) and CD3OD ( =
49.0, 13C) were references. CC: Silica gel 60, 
0.06 – 0.2 mm (Merck) for the first column; 
Sephadex LH-20 and silicagel 60, 40 – 63 µm
(Merck) for the following columns. TLC: sili-
cagel 60 F254 (Merck). 
2. Plant material 
Leaves of F. acuminatissima were collected 
in Nghe An province, Vietnam in November 
2004. The species was identified by Dr. Ngo 
Van Trai, Institute of Materia Medica, Hanoi. A 
voucher specimen is deposited in the Herbarium 
at the same Institute.  
3. Extraction and isolation 
The dried and powdered leaves of F. acumi-
natissima (1.4 kg) were extracted with 95% 
aqueous MeOH at room temperature. MeOH 
was evaporated in vacuo, and the aq. solution 
was partitioned with n-hexane followed by 
EtOAc and n-BuOH. The organic solutions were 
evaporated in vacuo to afford 50; 10 and 15 g 
extracts, respectively. The n-hexane extract was 
chromatographed over silica gel with gradient 
CHCl3/MeOH (95:530:70) to give 40 frac-
tions (Fr-1Fr-40). 
a) Catechin  (1)
The crude compound 1 (15 mg) was isolated 
649
from fraction 2 (Fr-2) by CC (sephadex LH-20, 
MeOH) and further purified by column chroma-
tography on silicagel (CHCl3-MeOH, 70:30); 
FT-IR (KBr) max, cm-1: 3405 (OH), 2924, 1612, 
1518, 1463, 1287, 1141; EI-MS 70 eV, m/z (rel. 
int.): 290 [M]+ (42), 271 (4), 152 (40), 139
Table 1: 1H- and 13C-NMR data of compounds 1 and 2 (125/500 MHz in CD3OD) 
1 2
Position 
C H C H
2 82.85 4.59, d (7.5) 158.91
3 68.81 3.99, m 135.46
4
28.50 ax 2.53, dd (16.1, 8.1) 
eq 2.87, dd (16.1, 5.4) 
179.36
5 157.56 163.02
6 96.33 5.95, d (2.3)  100.01 6.24, d (2.1)  
7 157.82 166.14
8 95.54 5.88, d (2.3) 94.94 6.44, d (2.1) 
9 156.91 158.54
10 100.86 105.70
1' 132.23 123.04
2' 115.28 6.86, dd (1.9) 116.13 7.96, d (2.1) 
3' 146.24 150.86
4' 146.22 148.36
5' 116.11 6.78, d (8.1) 114.60 6.94, d (8.5) 
6' 120.05 6.74, dd (8.1, 1.9) 124.02 7.65, dd (8.5, 2.1) 
Gluc 1''   102.52 5.25, d (7.4) 
2''   77.39 3.4 - 3.5, m 
3''  78.19 3.4 - 3.5, m 
4''   69.79 3.2 - 3.3, m 
5''   75.91 3.2 - 3.3, m 
6''  68.54 3.4 - 3.5, m 3.84 dd (1.5, 11.5) 
Rham 1''' 104.39 4.56, br s 
2'''   72.09 3.62, dd (1.6, 4.3) 
3'''   72.30 3.4 - 3.5, m 
4'''   73.85 3.4 - 3.5, m 
5'''   72.09 3.4 - 3.5, m 
6'''   17.87 1.12, d (6.2) 
OMe   56.81 3.97 s 
OH  4.56 br s   
NMR: Bruker Avance 500, 499.84 MHz (1H-) and 125 MHz (13C-, 13C-DEPT). TMS ( = 0.0, 1H) and 
CD3OD ( = 49.0, 13C) were references. CC: Silica gel 60, 0.06 - 0.2 mm (Merck) for the first column; 
Sephadex LH-20 and silica gel 60, 40 - 63 µm (Merck) for the following columns. TLC: silica gel 60 F254 
(Merck). 
 
(100), 123 (69), 110 (39), 97 (32), 55 (76); 1H- 
and 13C-NMR data, see table 1. 
b) Isorhamnetin-3-o-rutinoside (narcissoside, 2)
Compound 2 (18 mg) was isolated as brown 
powder from Fr26-28 by CC (sephadex LH-20, 
MeOH) and further purified by column chroma-
650
tography on silica gel (CHCl3-MeOH, 80:20); 
FT-IR (KBr) max: 3388, 2925, 1652, 1600, 
1506, 1451, 1358, 1061 cm-1; EI-MS 70 eV, m/z 
(rel. int.): 316 [M-gly]+ (100), 301 [M-Me]+
(15), 286 [M-30]+ (11), 153 (8), 128 (14), 85 
(19), 60 (26); 1H- and 13C-NMR data, see table 
1. 
III - Results and Discussion 
The flavonoids were obtained from the 
MeOH extract of the leaves via partition be-
tween n-hexane followed by EtOAc and n-
BuOH. The n-hexane extract was chromatogra-
phed over silica gel with gradient CHCl3-MeOH 
and further purified by column chromatography 
on silica gel to afford 1 and 2.
The molecular formula of compound 1
(C15H14O6) was deduced from combined analysis 
of EI-MS at m/z 290 [M]+, 1H- and 13C-DEPT 
NMR spectra (table 1). The EI-MS of 1 shows 
the base peak of the A-ring and the B-ring frag-
ments (m/z 139 and 152) due to a Retro-Diels-
Alder cleavage, indicating the presence of a fla-
van-3-ol with two hydroxy groups in each A- 
and B-ring [3]. The 1H-NMR spectrum exhib-
ited a doublet at  4.59 (H-2), two doublets of 
doublet multiplet at  3.99 (H-3), 2.53 (H-4ax), 
2.87 (H-4eq), as well as five aromatic protons. 
The 1H- and 13C-NMR spectrum data of 1 are 
identical with those in literature [4, 5]. Catechin 
and its analogs showed antitumor and antioxi-
dant activities [3, 4]. 
 
1: Catechin 
O
OH
HO
OCH3
OH
O
O--D-glc-(6''-1''')--L-rham
2: Isorhamnetin-3-o-rutinoside 
 
The EI-MS of compound 2 gave a peak at 
m/z 316 [M-glycone]+, combination with 13C-
NMR and DEPT spectra leading to the formula 
C16H12O7 for the aglycone. The aglycone moiety 
was identified as flavone-3-ol from the charac-
teristic of molecular formula and aromatic sig-
nals in the 1H- and 13C-NMR spectra. The 1H-
NMR spectrum showed one methoxy group 
(H3.97, C56.81) and five aromatic protons. The 
signals from H 3.3 - 5.3 are assigned of two 
sugar protons. The -D-glucopyranose was 
identified by anomeric signals at H5.25 (d, J = 
7.4 Hz) C104.39 and the rhamnopyranose was 
identified by methyl signal at H 1.12 (d, J = 6.2 
Hz) C17.87 (table 1). The 1H- and 13C-NMR 
spectra of sugar moiety were identical with 
those of quercetin-3-o-rutinoside [6] and the 
aglycon moiety were identical with those of 
isorhamnetin [7], therefore the structure of 2
was determined as 3-O--L-rhamnopyranosyl-
(16)--D-glucopyranyloxy-4',5,7-trihydroxy-
3'-methoxyflavone (isorhamnetin-3-o-rutino-
side, narcissoside). Isorhamnetin-3-o-rutinoside 
was isolated for the first time from the flowers 
of Narcissus tazetta and then was found in Lil-
ium aurantum, Herniaria glabra [6 - 8]. 
Acknowledgements: We thank the Vietnamese 
Ministry of Science and Technology (MOST), 
for financial support in form of a project in ba-
sic researches (2006-2007). We are indebted to 
Dr. Ngo Van Trai, Hanoi for the identification 
of the plant material. 
References 
1. Ban N. T., Thuc vat chi Vietnam (Flora of 
Vietnam), Hanoi Publishing House for Sci-
ence and Technics, P. 209 - 210 (2000). 
651
2. L. M. Perry. Medicinal Plants of Southeast 
Asia, MIT press Cambridge, P.19 (1980). 
3. P. Miketova, K. H. Schram, J. L. Withney, 
E. H. Kerns, S. Valcic, B. N. Timmermann, 
K. Volk. J. Nat. Prod., 61, P. 461 - 467 
(1998). 
4. Ninomaya, Unten, Kim. Properties of Green 
Tea Polyphenols, P. 30 (1988). 
5. Nonaka Gen-Ichiro, O. Kawahara, I. Nishi
oka. Chem. Pharm. Bull., 31 (11), P. 3906 - 
3914 (1983). 
6. K. Kazuma. Phytochemistry, 62, P. 229 – 
237 (2003). 
7. J. Y. Lallemand, M. Duteil. Org. Magn. 
Reson., 9, 179 (1977). 
8. H. Itokawa, Y. Oshida, A. Ikuta, H. Ina-
tomi, S. Ikegami. Phytochemistry, 20, 2421 
(1981). 
 


flavonoids from Fissistigma acuminatissima

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flavonoids from Fissistigma acuminatissima

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