Dihydrostilbene glycosides and lignan from Camellia sasanqua

Cite this paper: Vietnam J. Chem., 2020, 58(5), 661-665 Article 
DOI: 10.1002/vjch.202000062 
661 Wiley Online Library © 2020 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH 
 Dihydrostilbene glycosides and lignan from Camellia sasanqua 
Nguyen Thi Cuc1,2, Nguyen Xuan Nhiem1,2, Bui Huu Tai1,2, Phan Van Kiem1,2*, Vu Kim Thu3* 
1Graduate University of Science and Technology, Vietnam Academy of Science and Technology (VAST), 
18 Hoang Quoc Viet, Cau Giay district, Hanoi 10000, Viet Nam 
2Institute of Marine Biochemistry, VAST, 18 Hoang Quoc Viet, Cau Giay district, Hanoi 10000, Viet Nam 
3Hanoi University of Mining and Geology, Pho Vien, Duc Thang, Bac Tu Liem district, Hanoi 10000, 
Viet Nam 
Submitted April 27, 2020; Accepted May 17, 2020 
Abstract 
Three dihydrostilbene glycosides, 3,5-dihydroxydihydrostilbene 4′-O-β-D-glucopyranoside (1), 3,5-
dimethoxydihydrostilbene 4′-O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside (2), 5,4′-dihydroxydihydrostilbene 
3-O-β-D-glucopyranoside (3), and one lignan, nudiposide (4) were isolated from the methanol extract of leaves of 
Camellia sasanqua Thunb. Their chemical structures were determined by using ESI-MS and NMR spectra as well as in 
comparison with the reported data. Compounds 3 and 4 were reported from Camellia genus for the first time. 
Keywords. Camellia sasanqua, dihydrostilbene, lignan. 
1. INTRODUCTION 
Camellia sasanqua (Theaceae) is an evergreen shrub 
growing to 10m. The leaves are broad elliptic, 3-7 
cm long and 1.2-3 cm broad, with a finely serrated 
margin. The flowers are 5-7 cm in diameter, with 5-
8 white to dark pink petals.[1] Phytochemical studies 
revealed that this plant contained terpenoids and 
phenolics.[2-4] These compounds have shown the 
potential significant biological effects as anti-
inflammatory and anticancer activities.[2,3] This 
paper reported the isolation and structural 
elucidation of three known dihydrostilbene 
glycosides and one known lignan from the methanol 
extract of C. sasanqua leaves. 
2. MATERIALS AND METHODS 
2.1. Plant materials 
The leaves of Camellia sasanqua Thunb. were 
collected in Nguyen Binh, Cao Bang province, Viet 
Nam in April 2019, and identified by Dr. Nguyen 
The Cuong, Institute of Ecology and Biological 
Resources. A voucher specimen (NCCT-P85) was 
deposited at the Institute of Marine Biochemistry, 
VAST. 
2.2. General experimental procedures 
See reference: [8] 
2.3. Extraction and isolation 
The dried powder leaves of C. sasanqua (6.0 kg) 
were sonicated with hot MeOH (3 times × 15 L) to 
obtain MeOH extract (650 g) under reduced 
pressure. The MeOH extract was suspended in water 
and successively partitioned with n-hexane, 
dichloromethane (CH2Cl2), ethyl acetate (EtOAc) to 
yield corresponding n-hexane (CSA1A, 9.2 g), 
dichloromethane (CS1B, 95.0 g), ethyl acetate 
(CS1C, 54.0 g) residues, and water layer (CS1D). 
CS1D was chromatographed on a Diaion HP-20 
column, first eluting with water to remove sugar 
components, then increasing concentration of MeOH 
in water (25, 50, 75, and 100 %) to obtain four 
fractions, CS1D1-CS1D4. CS1D2 was 
chromatographed on a silica gel CC eluting with 
gradient solvent of CH2Cl2/MeOH (20/1, 10/1, and 
5/1, v/v) to give three fractions, CS1D2A-CS1D2C. 
CS1D2A was subjected on a RP-18 column eluting 
with acetone/water (1/3, v/v) to give three smaller 
fractions, CS1D2A1-CS1D2A3. CS1D2A1 was 
subjected to HPLC (J’sphere H-80 column, length 
250 mm × 20 mm ID, eluting with 18 % acetonitrile 
in water, a flow rate of 3 mL/min) to yield 
compound 4 (13.0 mg). CS1D2B was 
chromatographed on a RP-18 column eluting with 
MeOH/water (1/1.5, v/v) to give three fractions, 
CS1D2B1-CS1D2B3. CS1D2B1 was subjected to 
HPLC (J’sphere H-80 column, length 250 mm × 20 
Vietnam Journal of Chemistry Phan Van Kiem et al. 
© 2020 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 662 
mm ID, eluting with 22 % acetonitrile in water, a 
flow rate of 3 mL/min) to yield compounds 1 (60.0 
mg) and 3 (30.0 mg). The CS1D4 fraction was 
applied to a silica gel column, eluting with a 
gradient solvents of CH2Cl2/MeOH (20/1, 10/1, and 
5/1, v/v) to give three fractions, CS1D4A-CS1D4C.
 CS1D4B was chromatographed on a RP-18 column, 
eluting with MeOH/water (1/1, v/v) to give three 
smaller sub-fractions, CS1D4B1-CS1D4B3. 
Compound 2 (12.0 g) was obtained from CS1D4B3 
on a sephadex LH-20 column, eluting with 
MeOH/water (1/1, v/v). 
Figure 1: The chemical structures of compounds 1-4 
3,5-Dihydroxydihydrostilbene 4′-O-β-D-
glucopyranoside (1): white amorphous powder; 
[α]D25: -39.0 (c 0.1, MeOH); ESI-MS m/z 391 
[M-H]-; 1H- and 13C-NMR (CD3OD) data, see table 1. 
3,5-Dimethoxydihydrostilbene 4′-O-α-L-
rhamnopyranosyl-(1→6)-β-D-glucopyranoside 
(2): white amorphous powder; [α]D25: -63.0 (c 0.1, 
MeOH); ESI-MS m/z 565 [M-H]-; 1H- and 13C-NMR 
(CD3OD) data, see table 1. 
5,4′-Dihydroxydihydrostilbene 3-O-β-D-
glucopyranoside (3): white amorphous powder; 
[α]D25: -36.0 (c 0.1, MeOH); ESI-MS m/z 391 
[M-H]-; 1H- and 13C-NMR (CD3OD) data, see table 1. 
Nudiposide (4): white amorphous powder; 
[α]D25: -68.0 (c 0.1, MeOH); ESI-MS m/z 551 
[M-H]-; 1H-NMR (CD3OD) δH 2.70 (d, J = 6.0 Hz, 
H-1)/2.71 (d, J = 5.5 Hz, H-1), 1.73 (m, H-2), 2.06 
(m, H-3), 4.25 (d, J = 7.0 Hz, H-4), 6.43 (s, H-2′/H-
6′), 3.64 (m, H-2α), 3.62 (m, H-3α)/3.82 (m, H-3α), 
3.34 (s, 5-OMe), 3.87 (s, 7-OMe), 3.77 (s, 3′/5′-
OMe), Xyl: 4.12 (d, J = 7.5 Hz, H-1′′), 3.22 (dd, J = 
7.5, 9.0 Hz, H-2′′), 3.29 (t, J = 9.0 Hz, H-3′′), 3.52 
(m, H-4′′), 3.15 (dd, J = 10.5, 11.5 Hz, H-5′′)/3.87 
(m, H-5′′); 13C-NMR (CD3OD) δC 34.0 (C-1), 40.7 
(C-2), 46.9 (C-3), 43.3 (C-4), 147.6 (C-5), 138.9 (C-
6), 148.7 (C-7), 107.8 (C-8), 130.1 (C-9), 126.3 (C-
10), 139.6 (C-1′), 107.0 (C-2′/C-6′), 149.0 (C-3′/C-
5′), 134.6 (C-4′), 66.1 (C-2α), 71.2 (C-3α), 60.0 (5-
OMe), 56.6 (7-OMe), 56.8 (3′/5′-OMe), Xyl: 105.0 
(C-1′′), 75.0 (C-2′′), 78.0 (C-3′′), 71.3 (C-4′′), 67.1 
(C-5′′). 
3. RESULTS AND DISCUSSION 
Compound 1 was obtained as a white amorphous 
powder. The 1H-NMR spectrum of 1 showed the 
signals of four protons of a p-substituted aromatic 
ring at δH 7.01 (2H, d, J = 8.5 Hz) and 7.08 (2H, d, J 
= 8.5 Hz); three protons of an 1,3,5-trisubstituted 
aromatic ring at δH 6.13 (1H, d, J = 2.0 Hz) and 6.16 
(2H, d, J = 2.0 Hz); two methylene groups at δH 2.71 
(2H, t, J = 7.0 Hz) and 2.81 (2H, t, J = 7.0 Hz); and 
one anomeric proton at δH 4.88 (1H, d, J = 7.5 Hz). 
The 13C-NMR and HSQC spectra of 1 showed the 
signals of 20 carbons, including 5 non-protonateds at 
δC 137.1, 145.3, 157.2, and 159.2×2; 12 methines at 
δC 71.3, 74.9, 77.9×2, 101.2, 102.4, 108.1×2, 
117.6×2 and 130.3×2; and 3 methylenes at δC 37.8, 
39.1, and 62.5. The analysis of 1H- and 13C-NMR 
data suggested that structure of 1 was similar to 3,5-
dihydroxydihydrostilbene 4′-O-β-D-
glucopyranoside.[5] The position of hydroxy groups 
at C-3 and C-5 were confirmed by HMBC 
correlation from H-4 (δH 6.13) to C-2/C-6 (δC 
108.1)/C-3/C-5 (δC 159.2). The HMBC correlation 
between H-2′/H-6′ (δH 7.08) and C-1′ (δC 137.1)/C-4′ 
(δC 157.2)/C-α′ (δC 37.8), between glc H-1′′ (δH 
4.88) and C-4′ (δC 157.2) confirmed the position of 
β-D-glucopyranosyl at C-4′. Based on the above data 
Vietnam Journal of Chemistry Dihydrostilbene glycosides and lignin  
© 2020 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 663 
and ESI-MS result (m/z 391 [M-H]-, corresponding 
to the molecular formula of C20H24O8) the structure 
of compound 1 was determined as 3,5-
dihydroxydihydrostilbene 4′-O-β-D-
glucopyranoside. This compound was isolated from 
C. oleifera. [5] 
Table 1: The 1H- and 13C-NMR data for compounds 1-3 
C 1 2 3 
 δCa) δHa) (mult., J in Hz) δCa) δHa) (mult., J in Hz) δCa) δHa) (mult., J in Hz) 
1 145.3 - 145.3 - 145.6 - 
2 108.1 6.16 (d, 2.0) 107.6 6.32 (d, 2.0) 109.3 6.42 (dd, 1.5, 2.0) 
3 159.2 - 162.1 - 160.0 - 
4 101.2 6.13 (d, 2.0) 98.9 6.30 (d, 2.0) 102.7 6.40 (dd, 2.0, 2.0) 
5 159.2 - 162.1 - 159.2 - 
6 108.1 6.16 (d, 2.0) 107.6 6.32 (d, 2.0) 110.8 6.32 (dd, 1.5, 2.0) 
α 39.1 2.71 (t, 7.0) 39.4 2.82 (m) 39.4 2.76 (m) 
α′ 37.8 2.81 (t, 7.0) 37.9 2.83 (m) 37.9 2.79 (m) 
1′ 137.1 - 137.1 - 134.0 - 
2′, 6′ 130.3 7.08 (d, 8.5) 130.4 7.11 (d, 8.5) 130.4 6.98 (d, 8.5) 
3′, 5′ 117.6 7.01 (d, 8.5) 117.8 7.01 (d, 8.5) 116.0 6.69 (d, 8.5) 
4′ 157.2 - 157.3 - 156.3 - 
3,5-OMe 55.6 3.72 (s) 
Glc 
1′′ 102.4 4.88 (d, 7.5) 102.6 4.83 (d, 7.5) 102.2 4.82 (d, 7.5) 
2′′ 74.9 3.43 (dd, 9.0, 7.5) 74.9 3.47 (dd, 9.0, 7.5) 74.9 3.44 (dd, 8.5, 7.5) 
3′′ 77.9 3.48 (t, 9.0) 78.0 3.48 (t, 9.0) 78.0 3.47 (t, 9.0) 
4′′ 71.3 3.43 (t, 9.0) 71.5 3.37 (t, 9.0) 71.4 3.41 (t, 9.0) 
5′′ 77.9 3.49 (m) 76.8 3.55 (m) 78.0 3.41 (m) 
6′′ 62.5 3.73 (dd, 12.0, 5.0) 
3.91 (dd, 12.0, 1.5) 
67.9 3.63 (dd, 11.0, 6.0) 
4.03 (dd, 11.0, 2.0) 
62.5 3.73 (dd, 12.0, 5.0) 
3.91 (dd, 12.0, 1.0) 
Rha 
1′′′ 102.1 4.74 (d, 1.5) 
2′′′ 72.1 3.88 (dd, 1.5, 3.0) 
3′′′ 72.4 3.74 (dd, 3.0, 9.0) 
4′′′ 74.0 3.39 (t, 9.0) 
5′′′ 69.8 3.68 (m) 
6′′′ 17.9 1.24 (d, 6.5) 
a)recorded in CD3OD; Glc, glucopyranosyl; Rha, rhamnopyranosyl. 
Compound 2 was isolated as a white amorphous 
powder. Similar to 1, the 1H-NMR spectra of 2 
exhibited the signals of one dihydrostilbene, and two 
sugar moieties. The 13C-NMR and HSQC spectra of 
2 showed the signals of 28 carbons, including 5 non-
protonateds, 17 methines, 3 methylenes, 1 methyl, 
and 2 methoxy carbons. The analysis of 1H- and 13C-
NMR data of 2 were found to be similar to those of 
3,5-dimethoxydihydrostilbene 4′-O-α-L-rhamnopy-
ranosyl-(1→6)-β-D-glucopyranoside.[5] The HMBC 
correlations between H-4 (δH 6.30) and C-2/C-6 (δC 
107.6)/C-3/C-5 (δC 162.1), between methoxy group 
(δH 3.72) and C-3/C-5 (δC 162.1) confirmed the 
position of methoxy groups at C-3 and C-5. The 
HMBC correlations from H-2′/H-6′ (δH 7.11) to C-1′ 
(δC 137.1)/C-4′ (δC 157.3)/C-α′ (δC 37.9), from rha 
H-1′′′ (δH 4.74) to glc C-6″ (δC 67.9), and from glc 
H-1′′ (δH 4.83) to C-4′ (δC 157.3) indicated the sugar 
linkage as α-L-rhamnopyranosyl-(1→6)-β-D-
glucopyranosyl and at C-4′. Furthermore, the ESI-
MS of 2 exhibited an ion peak at m/z 565 [M-H]-, 
corresponding to the molecular formula of 
C28H38O12. Consequently, the structure of 2 was 
elucidated as 3,5-dimethoxydihydrostilbene 4′-O-α-
L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside. 
This compound was isolated from C. oleifera.[5] 
Compound 3 also was isolated as a white 
amorphous powder. The 1H-NMR spectrum of 3 
showed the signals of one dihydrostilbene and one 
sugar unit. The 13C-NMR and HSQC spectra of 3 
showed the signals of 20 carbons, of which, 14 
carbons assigned to one dihydrostilbene and 6 
Vietnam Journal of Chemistry Phan Van Kiem et al. 
© 2020 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 664 
carbons to one β-D-glucopyranosyl unit. The 
analysis of NMR and ESI-MS data of 3 suggested 
that structure of 3 was a dihydrostilbene glucoside, 
similar to 5,4′-dihydroxydihydrostilbene 3-O-β-D-
glucopyranoside.[6] The position of hydroxy groups 
at C-5 and C-4′ were confirmed by HMBC 
correlation from H-6 (δH 6.32) to C-2 (δC 109.3)/C-4 
(δC 102.7)/C-5 (δC 159.2), from H-2′/H-6′ (δH 6.98) 
to C-1′ (δC 134.0)/C-4′ (δC 156.3)/C-α′ (δC 37.9). 
13C-NMR data of the sugar from C-1′′ to C-6′′ were 
at δC 102.2, 74.9, 78.0, 71.4, 78.0, and 62.5, 
respectively, together with the coupling constant 
between H-1′′ and H-2′′, J = 7.5 Hz suggesting a β-
D-glucopyranoside. The HMBC correlation from glc 
H-1′′ (δH 4.82) to C-3 (δC 160.0) confirmed the 
position of β-D-glucopyranosyl at C-3. Thus, the 
structure of 3 was determined as 5,4′-
dihydroxydihydrostilbene 3-O-β-D-glucopyranoside. 
Figure 2: The key HMBC correlations of compounds 1-4 
The 1H-NMR spectrum of 4 showed the signals 
of two protons of a 1,3,4,5-tetrasubstituted aromatic 
ring at δH 6.43 (2H, s); one proton of a penta-
substituted aromatic ring at δH 6.59 (1H, s); four 
methoxy groups at δH 3.34 (3H, s), 3.77 (6H, s), and 
3.87 (3H, s); and one anomeric proton at δH 4.12 
(1H, d, J = 7.5 Hz). The 13C-NMR and HSQC 
spectra of 4 showed the signals of 27 carbons, 
including 9 non-protonateds, 10 methines, 4 
methylenes, and 4 methoxy carbons. The analysis of 
1H- and 13C-NMR data of 4 were found to be similar 
to those of with those of nudiposide.[7] The location 
of glucose unit at C-3α was determined by the 
downfield chemical shift of C-3α (δC 71.2) as well as 
by HMBC correlation between xyl H-1′′ (δH 4.12) to 
C-3α (δC 71.2). From the above evidence, compound 
4 was identified as nudiposide. 
4. CONCLUSION 
Three dihydrostilbene glycosides, 3,5-
dihydroxydihydrostilbene 4′-O-β-D-glucopyranoside 
(1), 3,5-dimethoxydihydrostilbene 4′-O-α-L-
rhamnopyranosyl-(1→6)-β-D-glucopyranoside (2), 
5,4′-dihydroxydihydrostilbene 3-O-β-D-
glucopyranoside (3), and one lignan, nudiposide (4) 
were isolated from the methanol extract of leaves of 
Camellia sasanqua Thunb. Their chemical structures 
were determined by using ESI-MS and NMR spectra 
as well as by comparison with the reported data. 
Compounds 3 and 4 were reported from Camellia 
genus for the first time. 
Acknowledgment. This research is funded by 
Graduate University of Science and Technology 
under grant number GUST.STS.ĐT2018-HH01. 
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Corresponding authors: 
Phan Van Kiem 
Institute of Marine Biochemistry, Vietnam Academy of Science and Technology 
18, Hoang Quoc Viet, Cau Giay district, Hanoi 10000, Viet Nam 
E-mail: phankiem@yahoo.com. 
Vu Kim Thu 
Hanoi University of Mining and Geology 
Pho Vien, Duc Thang, Bac Tu Liem district, Hanoi 10000, Viet Nam 
E-mail: vukimthu@humg.edu.vn.