Journal of the Chinese Chemical Society, 2008, 55, 863-870

863

Diversity of Chemical Constituents from Saxifraga montana H.

Jun-Xi Liu (

), Duo-Long Di* (

) and Yan-Ping Shi* (

Key Laboratory for Natural Medicine of Gansu Province, Lanzhou Institute of Chemical Physics,
Chinese Academy of Sciences, Lanzhou 730000, P. R. China

A thorough phytochemical investigation of the whole plant of Saxifraga montana H. afforded a new
glucoside, methyl 6-O-(E)-p-hydroxycinnamoxyl-glucosyringate (1), and seventeen known natural
products, 3-methyl-6-methoxy-3,4-dihydroisocoumarin-8-O-b-D-glucospyranoside (2), gallic acid (3),
glucosyringic acid (4), daphnoretin (5), chamaejasmoside (6), myricetin (7), quercetin (8), quercetin-3O-b-D-galactopyranoside (9), quercetin-3-O-a-L-arabinoside (10), quercetin-3-O-b-D-glucospyranoside (11), rutin (12), quercetin-3-O-b-D-glucopyranosyl (6-1) glucopyranoside (13), ursolic acid (14),
5,28-stigmastadien-3b-ol (15), b-sitosterol (16), b-daucosterin (17), 6-palmitoxyl-b-daucosterin (18).
On the basis of various spectroscopic methods, especially intensive 2D-NMR (COSY, HMQC and HMBC),
FAB-MS and HR-ESI-MS techniques, their structures were elucidated.
Keywords: Saxifraga montana; Saxifragaceae; Chemical constituents; Phenylpropanoids;
Dihydroisocoumarins.

INTRODUCTION
Saxifraga montana H., a perennial herbaceous plant
of the Saxifraga genus (Saxifragaceae), is widely distributed in the northwest of China.1 It has been used as a folk
medicine in Tibet for the treatment of headache, neuralgia,
influenza and cough.2 In order to find bioactive principles,
the chemical constituents of S. montana were systematically investigated. A new glucoside (1) and seventeen
known natural products (2-18) have been found from the
alcoholic extract of the whole plant of the above species.
While the structures of known compounds (3-18) were
identified by direct comparison of their spectral data (1H
NMR, 13C NMR and DEPT experiment) with those reported in the corresponding literature, compound 2 has
been identified through TLC in cultured carrot cells, but
the spectral data has not been reported.3,4 Compounds (1)
and (2) were elucidated by various spectroscopic methods
including intensive 2D-NMR (COSY, HMQC and HMBC),
FAB-MS and HR-ESI-MS techniques. Details of the isolation and structural determination of the compounds are described herein.
RESULTS AND DISCUSSION
The repeated chromatography of the alcoholic extract
of the title plant yielded eighteen compounds; 17 out of 18

were identified as known compounds: 3-methyl-6-methoxy-3,4-dihydroisocoumarin-8-O-b-D-glucospyranoside

(2), gallic acid (3),5 glucosyringic acid (4),6 daphnoretin
(5), 7 chamaejasmoside (6), 8 myricetin (7), 5,9 quercetin
(8),5,10~12 quercetin-3-O-b-D-galactopyranoside (9),10~12
quercetin-3-O-a-L-arabinoside (10),12 quercetin-3-O-bD-glucospyranoside (11),13 rutin (12),14 quercetin-3-O-bD-glucopyranosyl (6-1) glucopyranoside (13), 15 ursolic
acid (14),16 5,28-stigmastadien-3b-ol (15),17 b-sitosterol
(16),18,19 b-daucosterin (17),18,19 and 6-palmitoxyl-b-daucosterin (18).18 By various spectral techniques, including
IR, UV, 1H NMR, 13C NMR, DEPT, 2D-NMR (COSY,
HMQC, HMBC), FAB-MS and HR-ESI-MS experiments,
one of them was identified as a new compound, methyl 6O-(E)-p-hydroxycinnamoxyl-glucosyringate (1).
The FAB-MS spectrum of compound 1 gave quasimolecular ion peaks [M+H]+ at m/z 521, [M+Li]+ at m/z
527 and [M+Na]+ at m/z 543, as well as several significant
fragments at m/z 309 [M-211]+ for the loss of methyl syringate and 163 due to the loss of the methyl glucosyringate.
The MS, 13C NMR and DEPT data established its molecular formula to be C25H28O12, which could be supported by
HRESI-MS. Its UV spectrum showed absorption bands at
215, 264 and 295 nm indicating the presence of a highly
conjugated unsaturated system. The IR spectrum showed

* Corresponding author. Tel: +86-931-4968208; Fax: +86-931-8277088; E-mail: shiyp@lzb.ac.cn

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J. Chin. Chem. Soc., Vol. 55, No. 4, 2008

Liu et al.

Fig. 1. The structures of compounds 1-18.

absorptions for a hydroxyl group (3474, 3271 cm-1), conjugated ester (1719 cm-1), a,b-unsaturated carboxyl group
(1638 cm-1) and the aromatic rings (1604, 1514 and 1464
cm-1).
Careful analysis of the 1H and 13C NMR spectra of 1
indicates the signals could be due to three structural parts,
Part A: methyl syringate moiety,6 Part B: (E)-p-hydroxycinnamoxyl moiety,20 and Part C: a sugar moiety.

Part A (Fig. 2): The NMR signal features (Table 1)

suggested that part A could be a methyl syringate unit. 6
This conclusion was further supported by the results from
the HMBC experiment (Fig. 3): correlations of H-3 with
C-1 (dc 165.7), C-2 (dc 125.8), and C-5 (dc 138.6); H-7
with C-1, C-2, and C-5; H-OCH 3 (dc 51.7) with C-1; HOCH3 (dc 56.0) with C-4 and C-6 (dc 152.2 2). Thus, part
A was confirmed as a methyl syringate. Part B (Fig. 2): The

Diversity of Chemical Constituents from Saxifraga montana H.

J. Chin. Chem. Soc., Vol. 55, No. 4, 2008

865

Table 1. Data of 1H NMR (400 MHz), 13C NMR (100 MHz), DEPT and HMBC for
compound 1a,b
No

dH

Methyl syringate
1
2
3
7.29 (1H, s)
4
5
6
7
7.29 (1H, s)
3.90 (6H, s)
C-4, 6-OCH3
1-OCH3
3.90 (3H, s)
(E)-p-hydroxcinnamoxy
1
2
7.35 (1H, d, J = 8.8 Hz)
3
6.85 (1H, d, J = 8.8 Hz)
4
9.50 (OH, s)
5
6.85 (1H, d, J = 8.8 Hz)
6
7.35 (1H, d, J = 8.8 Hz)
7
7.55 (1H, d, J = 16.0 Hz)
8
6.23 (1H, d, J = 16.0 Hz)
9
Glucose
1
4.76 (1H, d, J = 6.4 Hz)
2
3.63 m
3
3.53 m
4
3.53 m
5
3.53 m
6
4.26 (1H, d, J = 2.0 Hz),
4.47 (1H, d, J = 2.0 Hz)

dC

HMBC

DEPT

165.7
125.8
106.6
152.2
138.6
152.2
106.6
056.0
051.7

H-3, 7, CH3O-1
H-3, 7
H-7
H-3, CH3O-4
H-1, 3, 7
H-7
H-3

C
C
CH
C
C
C
CH
CH3
CH3

125.0
129.3
115.6
159.3
115.6
129.3
144.5
113.6
166.7

H-3, 5, 8, 7
H-6, 7
H-2, 5
H-2, 3, 5, 6
H-6, 3
H-2, 7
H-2, 6, 8
H-7,
H-7, 8, 6

C
CH
CH
C
CH
CH
CH
CH
C

104.5
073.6
074.2
069.8
076.0
063.1

H-6
H-6

CH
CH
CH
CH
CH
CH2

In CDCl3 solution; assignments were aided by DEPT, HMQC and HMBC; chemical shifts
(d) are ppm; coupling constants (J) are Hz.
b
TMS as interstandard.

H NMR spectrum of 1 showed two doublet signals at d

7.35 (2H, J = 8.8 Hz) and 6.85 (2H, J = 8.8 Hz) due to a
1,4-disubstituted aromatic ring, two doublet signals at d
6.23 (1H, Jtrans = 16.0 Hz) and 7.55 (1H, Jtrans = 16.0 Hz) as-

cribable to a,b-unsaturated trans double bond, and a singlet at d 9.50 (can be exchanged by D 2O) as a hydroxyl
group. The above 1H NMR results together with 13C NMR

Fig. 2. The structural parts of compound 1.

Fig. 3. Key HMBC correlations in compounds 1 and 2.

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J. Chin. Chem. Soc., Vol. 55, No. 4, 2008

data (Table 1) suggested the presence of a (E)-p-hydroxycinnamoxyl moiety.20 This decision could be further elucidated by correlations H-7 with H-8, H-2 with H-3, H-5
with H-6 in 1H-1H COSY and H-7, 8 with C-9 (dc 166.7),
H-7 with C-1 (dc 125.0) and C-2, H-8 with C-1, OH-4
with C-3, C-4 and C-5 in the HMBC experiment (Fig. 3).
So, the structural part B, (E)-p-hydroxycinnamoxyl moiety, should be deduced. Part C (Fig. 2): Except for the signals of parts A and B, the left ones showed a substituted
sugar group (Table 1). Additionally, the anomeric proton at
d 4.76 (1H, H-1) and the J value (6.4 Hz) suggested the
sugar group was a b-D-glucospyranoyl moiety (-Glu).6
The above structural parts A, B and C could be attached by key correlations: H-1 (in part C) with C-5 (dc
138.6, in Part A) and H-6 (4.26, 4.47, in Part C) with C-9
(in Part B) in the HMBC experiment (Fig. 3). Consequently, compound 1 was methyl 6-O-(E)-p-hydroxycinnamoxyl-glucosyringate, and all of the data of 1H and 13C
also were completely assigned.
Compound 2 was obtained as colorless crystals from
Me2CO. Its molecular formula of C17H22O9 was confirmed
on the basis of the quasi-molecular ion peaks [M+Li]+ at
m/z 377 and [M+Na]+ at m/z 393 in FAB-MS, together with

Liu et al.

[M+Na]+ at m/z 393.1149 (calc. 393.1156 for C17H22O9Na)

in the HR-ESI-MS. The IR spectrum of 2 showed absorption bands for hydroxyl groups (3479, 3430 cm-1), ester
carbonyl (1706 cm-1) and aromatic groups (1609, 1575,
and 1447 cm-1), respectively. The UV spectrum showed
that the maximal absorption bands at 214 and 265 nm indicated the presented of an unsaturated system in this molecule.
The 1H NMR spectrum of 2 showed a methyl at d 1.35
(3H, d, J = 6.4 Hz), a methyoxyl at d 3.86 (3H, s) signal,
and typical ABX system signals at d 2.84 (1H, dd, Jgem =
16.4 Hz, Jcis = 11.0 Hz, H-4a), 3.05 (1H, dd, Jgem = 16.4 Hz,
Jtrans = 3.6 Hz, H-4b) and 4.63 (1H, m, H-3), together with
two doublet signals at d 6.60 (1H, d, J = 2.0 Hz) and 6.90
(1H, d, J = 2.0 Hz) assigned to meta substituted aromatic
protons (H-5 and H-7). All of the feature signals indicated
the carbon skeleton of 2 was a 3-methyl-6-methoxy-3,4dihydroisocoumarin derivation. Otherwise, a b-D-glucospyranoyl group was identified by the typical anomeric proton at d 4.84 (1H, d, J = 7.6 Hz) in 1H NMR and six carbon
signals in 13C NMR (Table 2).6 Aside from the signals of
the sugar, the 13C NMR spectrum (Table 2) gave 11 carbon
signals, including one methyl, one methyoxyl (dc 55.2),

Table 2. Data of 1H NMR (400 MHz), 13C NMR (100 MHz), DEPT and HMBC for
compound 2a,b
No
1
3
4
4a
5
6
7
8
8a
9
10
1
2
3
4
5
6
a

dH
4.63 (1H, m)
2.84 (1H, dd, J = 16.4, 11.0 Hz)
3.05 (1H, dd, J = 16.4, 3.6 Hz)
6.60 (1H, d, J = 2.0 Hz)
6.90 (1H, d, J = 2.0 Hz)

1.35 (3H, d, J = 6.4 Hz)

3.86 (3H, s)
4.84 (1H, d, J = 7.6 Hz)
3.49
3.47
3.42
3.54 (1H, m)
3.90 (1H, dd, J = 19.2, 2.4 Hz)
3.67 (1H, dd, J = 19.2, 2.4 Hz)

dC
162.5
073.7
035.0
143.2
107.8
164.5
102.9
161.2
107.6
019.4
055.2
103.2
073.7
077.4
076.3
070.2
061.6

HMBC
H-9, H-4
H-9, H-5
H-4
H-4, H-7
H-5, 7, CH3O-10
H-5
H-1, H-7
H-5

DEPT
C
CH
CH2
C
CH
C
CH
C
C
CH3
CH3
CH
CH
CH
CH
CH
CH2

In acetone-d6 solution; assignments were aided by DEPT, HMQC and HMBC; chemical
shifts (d) are ppm; coupling constants (J) are Hz.
b
TMS as interstandard.

Diversity of Chemical Constituents from Saxifraga montana H.

one methylene, three methines, and five quaternary carbons. By careful observations and comparisons, the 1H and
13
C NMR data for the carbon skeleton of 2 were similar to
the reported compound, 3-methyl-8-hydroxyl-3,4-dihydroisocourmin, which has been isolated from the Ceratocystis
species.21,22 The attachment of glucose was indicated by
the strong correlation between the H-1 with C-8 in the
HMBC (Fig. 3). The absolute configuration at C-3 (R) was
determined by comparison to the naturally occurring (R)enantiomer compounds.23 Thus, compound 2 was determined to be 3-methyl-6-methoxy-3,4-dihydroisocoumarin8-O-b-D-glucospyranoside.
EXPERIMENTAL SECTION
General Methods
Melting points were obtained on an X-4 Digital Display Micro-Melting point apparatus, and were uncorrected.
Optical rotations were taken on a polarimeter 341 (Perkin
Elmer) in MeOH solution. UV spectra were observed on a
Shimadzu UV-240 spectrophotometer in MeOH solution.
IR spectra were measured on a Nicolet NEXUS 670 FT-IR
spectrometer. 1H NMR (400 Hz), 13C NMR (100 Hz) and
2D-NMR were recorded on a Varian INOVA-400 MHzFT-NMR spectrometer with TMS as internal standard.
FAB-MS was obtained on a VG-ZAB-HS spectrometer.
HR-ESI-MS was recorded on a Bruker APEX II. Silica gel
(200-300 mesh) was used for CC and silica GF254 (10-40 m)
for TLC. Spots were detected on TLC under UV light or by
heating after spraying with 98% H 2SO 4 : EtOH = 5:95
(v:v).24,25
Plant Material
The whole plant of Saxifraga montana H. was collected at Huangzhong County, Qinghai Province, P. R.
China, in 2003, and identified by Prof. Guo-Liang Zhang,
Department of Biology, Lanzhou University, P. R. China. A
voucher specimen (No. ZY-03002) has been deposited at
the Key Laboratory for Natural Medicine of Gansu Province.
Extraction and Isolation
The air-dried and ground whole plant of S. montana
(5.0 kg) was extracted with 95% EtOH at room temperature
seven times (7 24 h) and the EtOH was removed under reduced pressure to give a residue (200.0 g), which was subjected to fractionation by column chromatography (CC)
over silica gel (200-300 mesh, 1500 g), eluting with a gradient of petroleum ether (60-90 C)-acetone (v:v = 50:1,
40:1, 30:1, 10:1, 5:1, 3:1, and 1:1; 500 mL for each eluent)

J. Chin. Chem. Soc., Vol. 55, No. 4, 2008

867

and finally with MeOH (2000 mL). According to differences indicated by TLC, 8 crude fractions [F1 (50:1, 20 g),
F2 (40:1, 30 g), F3 (30:1, 14 g), F4 (10:1, 7 g), F5 (5:1, 7 g),
F6 (3:1, 7.4 g), F7 (1:1, 5 g) and F8 (MeOH, 160 g)] were
obtained. F2 was separated on CC over silica gel (200-300
mesh, 300 g) with petrolum ether (60-90 C) -EtOAc (v:v,
20:1) and gave compound 14 (15 mg). F3 was then separated by CC on silica gel (200 g) with a gradient of petroleum ether (60-90 C)-EtOAc (v:v, 10:1, 8:1, 5:1) as eluent
to give several fractions. The eluate of petrolum ether (6090 C)-EtOAc (v:v, 8:1) was purified by petroleum ether
(60-90 C)-acetone (v:v, 5:1) giving compound 15 (10 mg)
and compound 16 (20 mg). F4 was purified by CC on silica
gel (30 g) and eluted repeatedly with petroleum ether (6090 C)-acetone (v:v, 6:1) to give impure 3 (10 mg), pure 18
(8 mg) and 5 (10 mg). The impure compound 3 was further
recrystalized by acetone to yield pure 3 (5 mg). F5 was purified by CC on silica gel (30 g) and eluted with petroleum
ether (60-90 C)-acetone (v:v, 4:1) to give impure 1 (16
mg), which was further purifed by silica gel column with
CHCl3-acetone (v:v, 12:1). F6 was purified by CC on silica
gel (30 g) and eluted repeatedly with petroleum ether (6090 C)-acetone (v:v, 4:1) to give compounds 2 (15 mg), 4
(10 mg), 6 (11 mg) and 17 (18 mg). F8 (MeOH, 160 g) was
subjected to isolation by CC over silica gel (800 g), using
CHCl3-EtOH (v:v, 10:1-1:2) as eluent to give subfractions
F8a, F8b, F8c. F8a was separated by CC on silica gel with
CHCl3-MeOH (v:v, 8:1) to produce compound 7 (11 mg)
and crude 8 (20 mg), which was repurified by MeOH. F8b
was separated by CC on silica gel with CHCl3-MeOH (v:v,
2:1-1:1) to produce compounds 9 (30 mg), 10 (20 mg), 11
(19 mg), 12 (30 mg) and 13 (18 mg).
Methyl 6-O-(E)-p-hydroxycinnamoxyl-glucosyringate
(1)
Colorless crystals (Me2CO); mp. 145-146 C; [a] 20
D =
-89 (c 0.14, MeOH); UV (MeOH) lmax (log e) 215 (2.56),
264 (2.54) and 295 (2.46) nm; IR (KBr) n 3474, 3271,
2948, 1719, 1638, 1604, 1514, 1464, 1416, 1225, 1132,
1079 cm-1; HRESI-MS m/z = 543.1469 [M+Na]+ , (calc.
543.1472 for C25H 28O 12Na); FAB-MS m/z 521 [M+H]+ ,
527 [M+Li]+, 543 [M+Na]+, 309 [M-211]+, 163 [M-357]+;
1
H and 13C NMR data: see Table 1.
3-Methyl-6-methoxy-3,4-dihydroisocoumarin-8-O-b-Dglucospyranoside (2)
Colorless crystals (Me2CO), mp. 149-150 C, [a] 20
D =
-41 (c 1.34, MeOH); UV (MeOH) lmax (log e) 214 (1.18),
265 (1.09); IR (KBr) n 3479, 3430, 2919, 1706, 1609,

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1575, 1447, 1343, 1264, 1086 cm-1; FAB-MS m/z 377 [M+
Li]+ , 393 [M+Na]+ ; HRESI-MS m/z 393.1149 [M+Na]+
(calc. 393.1156 for C17H22O9Na), 209.0803 [M-glu]+ (calc.
209.0814 for C11H13O4); 1H and 13C NMR data: see Table 2.
Gallic acid (3)
Colorless crystals (Me2CO), mp 211-212 C; 1H NMR
(400 MHz, DMSO-d 6) d: 12.20 (1H, br s, COOH), 9.16
(2H, br s, OH-3, 5), 8.80 (1H, s, OH-4), 6.90 (2H, s, H-2,
6); 13C NMR (100 MHz, DMSO-d6) d: 120.5 (C-1), 108.7
(C-2), 145.4 (C-3), 138.0 (C-4), 145.4 (C-5), 108.7 (C-6),
167.5 (COOH).
Glucosyringic acid (4)
Colorless crystals, mp 218-220 C (Me2CO); 1H NMR
(400 MHz, DMSO-d6) d: 7.21 (2H, s, H-2, 6); 5.09 (1H, d, J
= 8.0 Hz, glu-1), 3.83 (6H, s, 2 OCH3), 13C NMR (100
MHz, DMSO-d6) d: 125.7 (C-1), 107.3 (C-2), 152.4 (C-3),
138.1 (C-4), 152.4 (C-5), 107.3 (C-6), 166.9 (CO), 101.9
(C-1), 74.2 (C-2), 76.6 (C-3), 69.6 (C-4), 77.4 (C-5),
60.8 (C-6), 56.3 (CH3O 2).
Daphnoretin (5)
Colorless crystals, mp 245-246 C (ethanol), 1H NMR
(400 MHz, DMSO-d6) d: 10.02 (OH-7), 7.82 (1H, d, J = 9.6
Hz, H-4), 7.76 (1H, s, H-4), 7.56 (1H, d, J = 8.8 Hz, H-5),
7.00 (1H, dd, J = 8.8, 2.4 Hz, H-6), 6.98 (1H, s, H-5), 6.94
(1H, d, J = 2.4 Hz, H-8), 6.92 (1H, s, H-8), 6.30 (1H, d, J =
9.6 Hz, H-3), 3.91 (3H, s, CH3O); 13C NMR (100 MHz,
DMSO-d6) d: 159.6 (C-2), 137.1 (C-3), 130.5 (C-4), 109.9
(C-5), 146.0 (C-6), 150.7 (C-7), 103.1 (C-8), 147.6 (C-9),
114.1 (C-10), 160.1 (C-2), 113.4 (C-3), 143.4 (C-4),
129.4 (C-5), 114.5 (C-6), 156.9 (C-7), 104.1 (C-8),
155.0 (C-9), 114.5 (C-10), 56.1 (OCH3-6).
Chamaejasmoside (6)
Colorless crystals, mp 204-205 C (ethanol), 1H NMR
(400 MHz, DMSO-d6) d: 8.03 (1H, d, J = 9.6 Hz, H-4),
7.86 (1H, s, H-4), 7.71 (1H, d, J = 8.8 Hz, H-5), 7.27 (1H,
s, H-5), 7.23 (1H, s, H-8), 7.22 (1H, d, J = 2.4 Hz, H-8),
7.13 (1H, dd, J = 8.8, 2.4 Hz, H-6), 6.38 (1H, d, J = 9.6
Hz, H-3), 5.04 (1H, d, J = 5.6 Hz, H-1), 4.55 (2H, t, J =
5.4 Hz, H-6), 3.71 (3H, s, CH3O); 13C NMR (100 MHz,
DMSO-d6) d: 156.9 (C-2), 137.1 (C-3), 129.8 (C-4), 109.5
(C-5), 146.4 (C-6), 149.0 (C-7), 103.0 (C-8), 146.7 (C-9),
112.2 (C-10), 159.9 (C-2), 114.0 (C-3), 144.0 (C-4),
129.9 (C-5), 113.7 (C-6), 159.4 (C-7), 104.4 (C-8),
155.0 (C-9), 114.6 (C-10); glucose, 99.7 (C-1), 76.7 (C2), 73.1 (C-3), 69.6 (C-4), 77.1 (C-5), 60.6 (C-6), 56.0
(CH3O).

Liu et al.

Myricetin (7)
Yellow needle crystals, 352-355 C, 1H NMR (400
MHz, Me2CO-d6) d: 12.14 (OH-5), 7.39 (1H, s, H-2, 6),
6.49 (1H, d, J = 2.0 Hz, H-8), 6.25 (1H, d, J = 2.0 Hz, H-6);
13
C NMR (100 MHz, DMSO-d 6) d: 146.4 (C-2), 135.7
(C-3), 175.9 (C-4), 161.3 (C-5), 98.4 (C-6), 164.5 (C-7),
93.8 (C-8), 157.1 (C-9), 107.6 (C-10), 122.1 (C-1), 107.6
(C-2), 145.7 (C-3), 136.2 (C-4), 145.7 (C-5), 107.6
(C-6).
Quercetin (8)
Yellow needle crystals, 310-314 C; 1H NMR (400
MHz, DMSO-d 6) d: 12.48 (OH-5), 10.77 (OH-7), 9.58
(OH-3), 9.36 (OH-3), 9.30 (OH-4), 7.66 (1H, d, J = 2.4
Hz, H-2), 7.52 (1H, dd, J = 8.4, 2.4 Hz, H-6), 6.87 (1H, d,
J = 8.4 Hz, H-5), 6.39 (1H, d, J = 2.0 Hz, H-8), 6.17 (1H, d,
J = 2.0 Hz, H-6).
Quercetin 3-O-b-D-galactopyranoside (Hyperoside) (9)
Yellow crystals, 231-232 C, 1H NMR (400 MHz,
DMSO-d6) d: 12.62 (OH-5), 10.88 (OH-7), 9.73 (OH-3),
9.16 (OH-4), 7.67 (1H, dd, J = 8.4, 2.4 Hz, H-6), 7.52
(1H, d, J = 2.4 Hz, H-2), 6.81 (1H, d, J = 8.4 Hz, H-5),
6.39 (1H, d, J = 2.0 Hz, H-8), 6.17 (1H, d, J = 2.0 Hz, H-6),
galactopyranose: 5.37 (1H, d, J = 7.6 Hz, H-1); 13C NMR
(100 MHz, DMSO-d6) d: 156.9 (C-2), 133.4 (C-3), 177.7
(C-4), 161.2 (C-5), 98.7 (C-6), 164.2 (C-7), 93.6 (C-8),
156.4 (C-9), 104.0 (C-10), 121.7 (C-1), 115.5 (C-2),
145.1 (C-3), 148.5 (C-4), 115.9 (C-5), 122.0 (C-6),
galactopyranose, 101.8 (C-1), 71.2 (C-2), 73.2 (C-3),
67.9 (C-4), 75.8 (C-5), 60.1 (C-6).
Quercetin-3-O-a-L-arabinoside (10)
Yellow crystals, 227-230 C, 1H NMR (400 MHz,
DMSO-d6) d: 12.61 (OH-5), 10.88 (OH-7), 9.74 (OH-3),
9.27 (OH-4), 7.53 (1H, dd, J = 8.4, 2.4 Hz, H-6), 7.58
(1H, d, J = 2.4 Hz, H-2), 6.84 (1H, d, J = 8.4 Hz, H-5),
6.40 (1H, d, J = 2.0 Hz, H-8), 6.20 (1H, d, J = 2.0 Hz, H-6),
arabinose: 5.59 (1H, d, J = 10.8 Hz, H-1); 13C NMR (100
MHz, DMSO-d6) d: 156.4 (C-2), 133.4 (C-3), 177.7 (C-4),
161.2 (C-5), 98.7 (C-6), 164.2 (C-7), 93.6 (C-8), 157.0
(C-9), 104.0 (C-10), 121.0 (C-1), 115.5 (C-2), 145.1 (C3), 148.5 (C-4), 116.4 (C-5), 121.7 (C-6), arabinose:
107.8 (C-1), 82.1 (C-2), 76.9 (C-3), 85.8 (C-4), 60.6
(C-5).
Quercetin-3-O-b-D-glucospyranoside (11)
Yellow crystals, 234-236 C; 1H NMR (400 MHz,
DMSO-d6) d: 12.64 (OH-5), 10.86 (OH-7), 9.72 (OH-3),
9.21 (OH-4), 7.67 (1H, dd, J = 8.4, 2.4 Hz, H-6), 7.57

Diversity of Chemical Constituents from Saxifraga montana H.

(1H, d, J = 2.4 Hz, H-2), 6.82 (1H, d, J = 8.4 Hz, H-5),

6.39 (1H, d, J = 2 Hz, H-8), 6.19 (1H, d, J = 2 Hz, H-6), glucose: 5.45 (1H, d, J = 7.6 Hz, H-1). 13C NMR (100 MHz,
DMSO-d6) d: 156.2 (C-2), 133.3 (C-3), 177.5 (C-4), 161.2
(C-5), 98.7 (C-6), 164.1 (C-7), 93.5 (C-8), 156.3 (C-9),
104.0 (C-10), 121.2 (C-1), 115.5 (C-2), 144.8 (C-3),
148.5 (C-4), 116.2 (C-5), 121.6 (C-6), glucose: 100.8
(C-1), 74.1 (C-2), 76.5 (C-3), 70.0 (C-4), 77.6 (C-5),
61.0 (C-6).
Quercetin-3-O-rhamnoglucoside (rutin) (12)
Yellow crystals, mp 180-182 C; 1H NMR (400 MHz,
DMSO-d6) d: 7.55 (1H, d, J = 2.0 Hz, H-2), 7.54 (1H, dd, J
= 8.8, 12.0 Hz, H-6), 6.84 (1H, d, J = 8.8 Hz, H-5), 6.39
(1H, d, J = 1.6 Hz, H-6), 6.19 (1H, d, J = 1.6 Hz, H-8), glucose: 5.32 (1H, d, J = 7.2 Hz, H-1), 0.97 (2H, d, J = 6 Hz,
H-6), rhamnose: 5.10 (1H, d, J = 7.0 Hz, H-1); 13C NMR
(100 MHz, DMSO-d6) d: 156.4 (C-2), 133.2 (C-3), 177.3
(C-4), 161.2 (C-5), 98.7 (C-6), 164.1 (C-7), 93.6 (C-8),
156.6 (C-9), 103.9 (C-10), 121.1 (C-1), 115.2 (C-2),
144.7 (C-3), 148.4 (C-4), 116.2 (C-5), 121.5 (C-6), glucose: 101.2 (C-1), 74.1 (C-2), 76.4 (C-3), 69.9 (C-4),
75.8 (C-5), 67.0 (C-6), rhamnose: 100.7 (C-1), 70.5
(C-2), 70.3 (C-3), 71.8 (C-4), 68.2 (C-5), 17.7 (C6).
Quercetin-3-O-b-D-glucospyranosyl (6-1)-glucospyranoside (13)
Yellow crystals, mp 180-182 C; 1H NMR (400 MHz,
DMSO-d6) d: 12.61 (OH-5), 10.85 (OH-7), 9.72 (OH-3),
9.22 (OH-4), 7.57 (1H, d, J = 2.0 Hz, H-2), 7.55 (1H, dd, J
= 8.8, 2.0 Hz, H-6), 6.83 (1H, d, J = 8.8 Hz, H-5), 6.37
(1H, s, H-6), 6.17 (1H, s, H-8), glucose: 5.38 (1H, d, J = 7.2
Hz, H-1), glucose: 5.28 (1H, d, J = 7.0 Hz, H-1); 13C
NMR (100 MHz, DMSO-d6) d: 156.4 (C-2), 133.4 (C-3),
177.4 (C-4), 161.3 (C-5), 98.7 (C-6), 164.1 (C-7), 93.6
(C-8), 156.4 (C-9), 104.1 (C-10), 121.2 (C-1), 115.2 (C2), 148.5 (C-3), 144.8 (C-4), 116.3 (C-5), 121.7 (C-6);
glucose: 100.9 (C-1), 73.4 (C-2), 76.3 (C-3), 69.7 (C4), 76.4 (C-5), 68.1 (C-6); glucose: 104.1 (C-1), 74.0
(C-2), 76.5 (C-3), 69.6 (C-4), 76.5 (C-5), 60.7
(C-6).
Ursolic acid (14)
Colorless crystals, 258-260 C; 1H NMR (400 MHz,
CDCl3) d: 5.05 (1H, t, J = 3.6 Hz, H-12), 2.99 (1H, t, J = 7.8
Hz, H-3), 0.90 (3H, s), 0.80 (3H, s), 0.76 (3H, s), 0.75 (3H,
s), 0.68 (3H, s), 0.65 (3H, s), 0.55 (3H, s); 13C NMR (100
MHz, CDCl3) d: 38.6 (C-1), 27.6 (C-2), 78.1 (C-3), 38.6
(C-4), 54.8 (C-5), 17.9 (C-6), 32.6 (C-7), 39.6 (C-8), 47.1

J. Chin. Chem. Soc., Vol. 55, No. 4, 2008

869

(C-9), 38.2 (C-10), 22.8 (C-11), 124.8 (C-12), 137.9 (C13), 41.6 (C-14), 27.8 (C-15), 23.8 (C-16), 47.1 (C-17),
52.3 (C-18), 40.1 (C-19), 38.4 (C-20), 30.3 (C-21), 36.5
(C-22), 27.8 (C-23), 15.0 (C-24), 15.4 (C-25), 16.6 (C-26),
23.1 (C-27), 179.5 (C-28), 16.7 (C-29), 20.8 (C-30).
5,28-Stigmastadien-3b-ol (15)
Colorless crystals, 1H NMR (400 MHz, CDCl3) d:
5.78 (1H, m, H-6), 5.18 (1H, dd, J = 5.0, 2.0 Hz, H-29),
5.19 (1H, dd, J = 16.0, 2.0 Hz, H-29), 5.12 (1H, ddd, J =
16.0, 5.0, 2.0 Hz, H-28), 3.53 (1H, m, H-3), 1.56 (s, H-19),
0.98 (3H, s, H-21), 0.95 (1H, m, H-26), 0.85 (3H, m, H-27),
0.65 (3H, s, H-18); 13C NMR (100 MHz, CDCl3) d: 37.2
(C-1), 31.7 (C-2), 71.8 (C-3), 42.3 (C-4), 140.7 (C-5),
121.7 (C-6), 31.9 (C-7), 31.9 (C-8), 50.1 (C-9), 31.5
(C-10), 21.1 (C-11), 39.7 (C-12), 34.8 (C-13), 56.7 (C-14),
24.3 (C-15), 28.2 (C-16), 55.8 (C-17), 11.8 (C-18), 19.4
(C-19), 36.1 (C-20), 16.5 (C-21), 34.5 (C-22), 26.0 (C-23),
35.9 (C-24), 29.0 (C-25) , 18.8 (C-26), 17.6 (C-27), 142.6
(C-28), 112.9 (C-29).
b-Sitosterol (16) and b-daucosterin (17)
Physical constants and spectral data were in accordance with the authentic samples.
6-Palmitoxyl-b-daucosterin (18)
Colorless crystals, 1H NMR (400 MHz, CDCl3) d:
5.34 (1H, brs, H-6), 0.65 (3H, s, H-18), 0.78 (3H, s, H-19),
0.88 (3H, d, J = 6.4 Hz, H-21), 0.86 (3H, s, H-26), 0.98
(3H, s, H-27), 0.79 (3H, d, J = 2.4 Hz, H-29), glucose: 4.37
(1H, d, J = 20 Hz, H-1), 3.34 (1H, m), 3.67 (1H, m), 3.42
(1H, m), 4.27 (1H, dd, J = 10.0, 2.0 Hz, H-6), 4.40 (1H, dd,
J = 10.0, 2.0 Hz, H-6), 0.83 (3H, s, CH3-palmitoxyl); 13C
NMR (100 MHz, CDCl3) d: 37.2 (C-1), 34.2 (C-2), 70.1
(C-3), 38.9 (C-4), 140.3 (C-5), 122.1 (C-6), 31.9 (C-7),
31.8 (C-8), 50.1 (C-9), 36.7 (C-10), 21.0 (C-11), 39.7 (C12), 42.3 (C-13), 56.7 (C-14), 24.3 (C-15), 28.2 (C-16),
56.1 (C-17), 11.8 (C-18), 19.3 (C-19), 36.1 (C-20), 18.8
(C-21), 33.9 (C-22), 26.0 (C-23), 45.8 (C-24), 29.2 (C-25),
19.8 (C-26), 19.0 (C-27), 23.0 (C-28), 11.9 (C-29), glucose: 101.2 (C-1), 73.5 (C-2), 76.0 (C-3), 70.1 (C-4),
73.8 (C-5), 63.3 (C-6), palmitoxyl: 174.6 (C-1), 29.7,
29.7 12, 29.6, 29.6, 29.3 (C-2), 14.1 (C-18).
ACKNOWLEDGMENTS
This research project was supported by the Foundation for the Bairen Jihua of the Chinese Academy of Sciences (CAS) in 2006 and the National Natural Science
Foundation of China (No. 20475057) and the 863 project
of the Ministry of Science and Technology of China (No.

870

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2007AA09Z403); we are also grateful to Professor Guoliang Zhang for his help in identification of the plant
material.
Received December 13, 2007.
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