Xanthones from Swertia punctata

Article abstract of DOI:10.1016/S0031-9422(02)00231-5

Isolation of 1-O-primeverosyl-3,8-dihydroxy-5-methoxyxanthone and 1-O-gentiobiosyl-3,7-dimethoxy-8-hydroxyxanthone, along with five known xanthones, isobellidifolin, methylbellidifolin, isoswertianin, methylswertianin and norswertianin-1-O-β-D-glucoside,

Full text of DOI:10.1016/S0031-9422(02)00231-5

Phytochemistry 61 (2002) 415–420
www.elsevier.com/locate/phytochem
Xanthones from Swertia punctata
a
ˇ
a
a
Nebojs
Nenad Juranic
a Menkovic , Katarina Savikin-Fodulovic , Vanja Bulatovic , Ivana Aljancic
ˇ ´ ´ ´ ˇ ´
d,
c
c
b
d,
´
, Slobodan Macura , Vlatka Vajs , Slobodan Milosavljevic *
´
aInstitute for Medicinal Plant Research ‘‘Dr. Josif Pan c˘ i c´ ’’, Tadeusˇa K o ˇsc´ usˇka 1, 11000 Belgrade, Yugoslavia
bInstitute for Chemistry, Technology and Metallurgy, Njegosˇeva 12, 11000 Belgrade, Yugoslavia
cDepartment of Biochemistry and Molecular Biology, Mayo Foundation, 200 First Street, SWGugg. CL009B, Rochester, MN 55905, USA
dFaculty of Chemistry, University of Belgrade, Studentski trg 16, PO Box 158, 11001 Belgrade, Yugoslavia
Received 21 March 2002; received in revised form 11 June 2002
Abstract
Isolation of 1-O-primeverosyl-3,8-dihydroxy-5-methoxyxanthone and 1-O-gentiobiosyl-3,7-dimethoxy-8-hydroxyxanthone, along
with five known xanthones, isobellidifolin, methylbellidifolin, isoswertianin, methylswertianin and norswertianin-1-O-b-d-glucoside,
from the roots of Swertia punctata is reported. In the aerial parts four xanthones, bellidifolin, methylbellidifolin, swertianolin and
mangiferin, and flavone-C-glucoside, isoorientin were identified. The chemotaxonomic and pharmacological significance of these
results is discussed.
#
2002 Elsevier Science Ltd. All rights reserved.
Keywords: Swertia punctata; Gentianaceae; Tetraoxygenated xanthones; 1-O-Primeverosyl-3,8-dihydroxy-5-methoxyxanthone; 1-O-Gentiobiosyl-
3,7-dimethoxy-8-hydroxyxanthone
1
. Introduction
co-occurring secoiridoids and flavone-C-glucosides. The
oxidation pattern of xanthones is generally uniform
within a particular section and is of prime importance
for chemotaxonomy.
Due to numerous pharmacological properties of its
constituents, genus Swertia, comprising ca. 170 species,
has received considerable attention so far (Neerja et al.,
2
such as S. japonica, S. chirata, S. hookeri, S. macro-
sperma, S. petiolata and S. calycina have been used in
traditional medicine of the Far East for many years.
Among their active principles xanthones (mostly
Among the Europaean Swertia species, only S. per-
ennis is officially recognized, whereas to S. punctata
Baumg. (together with S. alpestris and S. obtusa) a pro-
visional status has been assigned (Tutin, 1972). On the
other hand, Vladimirov and Tan (1998) claimed recently
that S. punctata growing on the moisty terrains of the
Western Stara Planina mountain, situated between Bul-
garia and Yugoslavia, is the well and precisely defined
plant species differing from S. perennis occuring in Rila,
Vitosha and Pirin mountains (Bulgaria). S. punctata is
000; Peres et al., 2000). Some members of the genus
1
,3,7,8- and 1,3,5,8-tetraoxygenated) occupy an impor-
tant role, exhibiting various activities, e.g. anti-
depressant, antileukaemic, antitumor, antitubercular,
choleretic, diuretic, antimicrobial, antifungal, anti-
inflammatory, antiviral, cardiotonic, hypoglycaemic,
etc. (Neerja et al., 2000; Basnet et al., 1994). The study
of xanthones, the secondary metabolites occurring in a
limited number of families, is also interesting from a
chemosystematic point of view. They were found to be
more useful chemotaxonomic markers in comparison to
also described by Jovanovic
species of the genus occurring in Serbia.
Our preliminary LC/DAD investigations (Savikin-
Fodulovic et al., 2002) of the xanthone content of
-Dunjic (1973) as the only
´ ´
ˇ
´
S. punctata originating from Stara Planina, revealed a
number of 1,3,7,8- and 1,3,5,8,-tetraoxygenated xan-
thones in roots and also in the aerial parts (Fig. 1). Due
to a possible chemosystematic and pharmacological
importance of these findings, we have repeated more
thoroughly the investigation of both aerial parts and roots
of S. punctata collected at the same locality as before.
*
Corresponding author. Tel.: +381-11-630-474; fax: +381-11-
36-061.
E-mail address: smilo@chem.bg.ac.yu (S. Milosavljevic
6
0
´
).
031-9422/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0031-9422(02)00231-5

416
N. Menkovi c´ et al. / Phytochemistry 61 (2002) 415–420
Table 1
UV maxima, nm (log "), of 4 and 8
Compound MeOH +NaOAc
+AlCl
3
3
+AlCl /HCl
4
235 (4.18) 248 sh
78 (3.92)
14 (3.88)
67 (3.48)
250 (4.04)
265 (3.99)
356 (4.03)
256 (4.05)
289 (4.02)
347 (3.95)
433 (3.32)
241 (4.07)
288 (3.97)
342 (3.89)
430 (3.23)
2
3
3
8
240 (4.90)
267 (3.90)
311 (3.76)
379 (2.84)
244 (3.79)
280 (3.91)
341 (3.79)
430 (2.91)
243 (3.85)
280 (3.90)
338 (3.78)
430 (2.93)
2
3
3
68 (3.83)
12 (3.70)
77 (2.96)
The similar procedure applied on the MeOH extract of
the aerial parts revealed four xanthones, bellidifolin (1)
(
(
Ishimaru et al., 1990; Basnet et al., 1994), swertianolin
5) (Kaldas et al., 1974; Ishimaru et al., 1990), mangi-
ferin, (10), and 3, together with flavone, isoorientin (11)
Hostettmann and Jacott-Guillarmod, 1976; Bellmann
(
and Jacot-Guillarmod, 1973). Compounds 1–3, 5–7, 9
and 11 were identified by comparison of their spectral
data to those published. Mangiferin (10) was identified
by LC/DAD of the crude extract using coinjection
(
viously from Gentiana lutea (Menkovic et al., 2000) and
tR=24.44 min) of the standard sample isolated pre-
´
identified by spectral data. Among the isolated com-
pounds, 7 and 9 were found previously in the roots,
while xanthones 1, 5 and 10, together with flavone 11
were identified previously in the aerial parts of S. per-
ennis (Rivaille et al., 1969; Hostettmann and Jacot-
Guillarmod, 1976).
Compound 4, a yellow crystalline material, showed in
+
+
ESIMS [M+H] , [M+Na] and [M+K]+ ions at m/z
569, 591 and 607, respectively, corresponding to mol-
ecular formula C H O . The UV absorption of 4
2
5
28 15
(Table 1) was typical for 1,3,5,8-tetraoxygenation. This
type of substitution was also confirmed by the H NMR
1
data (Table 2) containing resonances of two meta (d
6.69, H-2 and d 6.52, H-4; J2,4 =2.4 Hz) and two ortho-
coupled protons (d 7.37, H-6 and d 6.66, H-7; J6,7=9.0
Hz). The observed bathochromic shift of band at 314
nm to 356 nm with the increase in intensity revealed free
Fig. 1. Xanthones isolated from the aerial parts and roots of Swertia
punctata.
OH group at C-3 (Correˆ a et al., 1970). The presence of
an additional (chelated) phenolic OH (at C-1 or C-8)
2
. Results and discussion
was evident from a low field singlet (ꢀ 12.55) and the
bathochromic shifts observed in the UV spectrum in the
presence of AlCl /HCl (Table 1). The H NMR further
3
1
A combination of different preparative chroma-
tographic techniques applied on MeOH extracts of the
roots afforded five tetraoxygenated xanthones, iso-
bellidifolin (2) (Terreaux et al., 1995), methylbellidifolin
revealed signals of a methoxy group (ꢀ 3.86) and a dis-
accharide moiety. Acid catalyzed hydrolysis of 4, yielding
1,3,8-trihydroxy-5-methoxyxanthone (isobellidifolin, 2),
also isolated from this extract, indicated C-5 as the
position bearing the methoxy group. This was also sup-
ported by the occurrence of NOE (in NOESY) and
ROE (in ROESY) between the methoxy protons and
H-6. Additional evidence of 5-methoxy substitution was
gained from HMBC correlation between the methoxy
(3) (Ishimaru et al., 1990; Basnet et al., 1994; Miana and
El-Hazimi, 1984), isoswertianin (6) (Terreaux et al. 1995;
Gottlieb et al., 1970), methylswertianin (7) (Terreaux et
al., 1995; Basnet et al., 1994; Miana and El-Hazimi,
1984) and norswertianin-1-O-b-d-glucoside (9) (Hos-
tettmann et al., 1974) together with two new xanthones.

N. Menkovi c´ et al. / Phytochemistry 61 (2002) 415–420
417
Table 2
1H (500 MHz) and 13C (50 MHz) NMR data of 4 and 8 in DMSO-d
Xanthone 8, obtained as yellow crystals, exhibited in
ESIMS [M+H]+ and [M+Na]+ ions at m/z 613 and
a
6
635, respectively, corresponding to molecular formula
C H O . The UV absorption of 8 (Table 1) was typi-
cal for 1,3,7,8-tetraoxygenated xanthone, the substitu-
tion pattern, usual in Swertia (Neerja et al., 2000). The
H/C
4
8
2
7
32 16
ꢀ
H
ꢀ
C
ꢀ
H
ꢀ
C
1
2
3
4
–
159.4
100.0
164.9c
96.5
–
159.5b
99.1
6.69, d (2.4)
6.52, d (2.4)
6.80, d (2.4)
6.76, d (2.4)
1
H NMR spectrum of 8 (see Table 2), exhibiting signals
of four protons, two meta (ꢀ 6.76, H-2 and ꢀ 6.80, H-4;
J2,4=2.4 Hz) and two ortho-coupled (ꢀ 6.93, H-5 and ꢀ
–
–
–
166.0
94.9
4
5
6
7
8
8
9
9
1
a
–
–
159.0
139.3
119.5d
159.3b
104.9c
120.6
142.7
150.5
108.8
6.93, d (9.0)
7.46, d (9.0)
7
.46, H-6; J5,6=9.0 Hz), also confirmed this type of
7.37, d (9.0)
6.66, d (9.0)
1
108.9b
substitution. The H NMR spectrum also revealed two
methoxy groups (ꢀ 3.93 and 3.83), a chelated phenol
hydroxyl (ꢀ 13.31) and a disaccharide moiety containing
six doublets of secondary hydroxyls (ꢀ 4.8–5.5) and a
–
–
–
–
–
–
–
–
–
–
–
154.0
108.5b
a
179.9
104.3c
181.5
104.9c
a
0a
144.1
56.9
148.4
triplet (ꢀ 4.45, J=6.0 Hz) of a primary hydroxyl
00
OMe
OH
3.86, s
3.93, s, 3.83, s
13.31, s (8-OH)
56.7, 56.5
(6 -OH). Two anomeric protons were detected as
doublets (J ca. 7.5 Hz) at ꢀ 5.13 (H-1 ) and 4.23 (H-1 ).
12.55, s (8-OH)
0
00
Glc-1
0
1
13
The H NMR, together with the C NMR spectrum
(Table 2), containing 12 signals of the sugar residue at
the chemical shifts similar to those reported for xan-
thone gentiobiosides (Otsuka, 1999), indicated the
gentiobiosyl structure of this group. This was also con-
firmed by acid-catalysed hydrolysis yielding glucose. The
aglycone obtained by the hydrolysis was identified as 7,
also isolated from the same extract. The 3,7-dimethoxy
pattern was also in accordance with NOEs of the
methoxy groups to ortho-positioned protons, one of
them (at higher field) dipolarly coupled to H-6 and the
other to H-4. The NOE observed between H-2 and the
1
4.95, d (7.8)
102.0
5.13, d (7.5)
100.8
0
2
3.40, dd (4.2, 7.8, 8.4) 73.0
3.44, ddd (4.0, 7.5, 8.5) 73.5
3.32b
76.6
0
0
0
0
3.32b
3.30b
3
4
5
6
76.4
69.8
76.3
3.25, ddd (5, 9.0, ꢀ9.0) 69.8
3.55, m
3.74 brdd (ꢀ8, 9.0)
75.8
69.0
(A) 3.63, dd (6.0, 11.4);
68.7 (A) 3.65;b (B) 4.00,
(
B) 3.95, brd (11.4)
brd (10.0)
Glc-2
0
0
0
0
0
0
0
0
0
0
0
0
1
2
3
4
5
6
4.23, d (7.5)
103.9
2.97, ddd (4.5, 7.5, ꢀ8) 73.7
3.13, ddd (5.0, ꢀ8, ꢀ8) 76.9
3.06b
3.06b
70.3
77.1
61.2
(A) 3.43, ddd (5.5,
.0,11.0); (B) 3.65b
6
0
anomeric proton of the inner glucose unit (H-1 ) indi-
cated a 1-O-gentiobioside structure. The UV data
Xyl
0
0
0
0
0
0
0
0
0
0
104.2c
1
2
3
4
5
4.18, d (7.8)
3.00, dd (7.2)
73.6
76.5
69.8
measured in the presence of shift reagents (NaOAc and
AlCl /HCl, Table 1) are also in agreement with the
3.08, brdd (7.8, 7.8)
b
3
ꢀ3.30
hydroxyl at peri-position (C-1). According to the above
evidence, the structure of 8 was assigned as 1-O-gentio-
biosyl-3,7-dimethoxy-8-hydroxyxanthone.
(A) 2.98, dd (11.4, 11.4); 65.8
(
B) 3.68, dd (5.4, 11.4)
OHd
5
.06, d (4.2), 5.15, d
5.4), 5.16, d (5.4),
.91, d (4.8), 4.93 brs
5.18, d (4.5), 5.17, d
(
(5.0), 5.13, d (4.0),
4.92, d (5.0), 4.89, d
2.1. Chemotaxonomic and pharmacological significance
4
(
4.5), 4.83, d (4.5),
.45, t (6.0)
4
According to Neerja et al. (2000), 79 simple oxy-
a
genated xanthones have been isolated from the genus
Swertia till the end of 1998. They contained three types
of substituents, namely OH, OMe and O-sugar. The
only exception is mangiferin (10), bearing a C-glucose
unit, and occurring in a large number of families. They
are divided in three groups: trioxygenated (9%), tetra-
oxygenated (64%) and pentaoxygenated (27%). The
eight positions in their skeleton are substituted with
following abundances: C-1 (100%), C-2 (13%), C-3
(95%), C-4 (28.2%), C-5 (41%), C-6 (6.5%), C-7 (58%)
and C-8 (77%). The oxygenation pattern, i.e. 1,3,5,8-
and 1,3,7,8-tetrasubstitution, in the xanthones isolated
from S. punctata fits very well to these. As far as the
type of substitution is concerned the xanthone complex
of S. punctata is quite similar to that of the previously
studied S. perennis, originating from French (Rivaille et
Assigned by means of DQF COSY, PS NOESY, TOCSY, HSQC and
HMBC and the analogy with 1H NMR data of the related compounds.
b
Overlapped signals.
c
Not visible in 13C{ H} NMR spectrum; detected via HSQC and/or HMBC.
1
d
OH signals of both sugar units.
protons and C-5 (ꢀ 139.3). The sugar residue of 4 show-
1
3
ing 11 signals in the C NMR spectrum was identified as
primeverosyl by the similarity of 13C chemical shifts
(Table 2) to those reported for xanthone heterozides
bearing this group (Otsuka, 1999). The NOE of the
anomeric proton (H-1 ) of the glucose subunit (ꢀ 4.95 d,
J=7.8 Hz) to H-2, as well as HMBC correlation of
between H-1 and C-1 (ꢀ 159.4) were in accordance with
the attachment of the primeverosyl moiety to the oxygen
0
0
at C-1. Consequently the structure 4 was assigned as
1
-O-primeverosyl-3,8-dihydroxy-5-methoxyxanthone.

418
N. Menkovi c´ et al. / Phytochemistry 61 (2002) 415–420
al., 1969; Rivaille and Raulais, 1969) and Swiss Alps
Hostettmann and Jacot-Guillarmod, 1976; Hostett-
mann and Miura, 1977).
3.3. Extraction and isolation of the compounds
(
3.3.1. Roots
As reviewed by Neerja et al. (2000) xanthones 1, 3, 7
and 10 exhibited various biological activities such as:
hypoglycemic (1,3,7), hepatoprotective (1,3), anti-
tuberculous (7), antioxidant (7), antimalarial (7) and
antiinflammatory (10). This makes S. punctata attrac-
tive as a source of medicinal raw material, but since its
population is scarce and endangered, as reported
Air-dried roots (75 g) were extracted twice at room
temperature with MeOH (2ꢁ300 ml) for 24 h. The
combined extracts were concentrated in vacuo to yield
oily brown residue (R, 19.1 g) which was suspended in
water (150 ml). Successive extraction with Et O (3ꢁ120
2
ml), EtOAc (3ꢁ120 ml), and n-BuOH (3ꢁ120 ml)
afforded, after evaporation in vacuo fractions RE (1.2
g), RA (0.4 g) and RB (3.2 g), respectively. After eva-
poration of the water layer the residue RW (14.2 g) was
obtained. Only RE and RB, containing appreciable
recently in the Red Book of Serbian Flora (Jovanovic
999), our efforts are now concentrated in finding out
an alternative way for biomass production.
´
,
1
content of xanthones and flavones (according to 1
H
NMR) were further analyzed. All isolated known com-
pounds were identified by comparison of their spectral
data to those published. RE (1.1 g) was divided into six
3
. Experimental
3
.1. General
fractions (RE1 ) by DCFC on silica gel, starting elution
ꢂ6
with toluene/EtOAc (9.5:0.5) and gradually increasing
the polarity by addition of EtOAc (up to 7:3). Fractions
RE and RE (toluene/EtOAc, 8:2) were identified as 3
The spectra were recorded with the following instru-
ments: IR, Perkin-Elmer FT-IR Spectrometer 1725 X;
3
5
1H and 13C NMR 1D and 2D NMR, Varian Gemini
(21 mg) and 7 (42 mg). Fraction RE (80 mg), contained
4
1
2
000 (200 MHz for H) and Bruker AMX 500 (500
1:1 mixture of 3 and 7. DCFC on silica gel of RE (84
6
1
MHz for H); UV, G113AA HP 8543 advanced UV-Vis
spectrometer; DCIMS (150 eV, isobutane), Finnigan
MAT Mass Spectrometer 8230, double focusing (BE
mg, eluted with toluene/EtOAc 7:3), using toluene/
EtOAc (9.5:0.5–9:1) afforded four subfractions (RE ).
1
ꢂ4
6
3
6
RE (35 mg, toluene/EtOAc, 9:1), after MPLC on silica
gel (column size A, same eluent, 5 ml/min) yielded 2 (7.6
geometry); ESIMS (a sample, dissolved in MeOH–H O,
2
4
6
1
:1) Finnigan MAT 900, double focusing (EB geometry)
mg), t between 35 and 40 min, as yellow gum. RE (15
R
equipped with a Finnigan MAT electrospray interface.
Optical rotations, Perkin-Elmer 141 MC polarimeter.
Melting points (not corrected), Boetius PHMK appara-
tus. Analytical HPLC, Hewlett Packard HPLC model
mg, toluene/EtOAc, 9:1) was purified by PTLC on silica
gel to yield 6 (2 mg), in form of yellow gum. RB (3.1 g)
was divided into four fractions (RB1 ) by DCFC on
ꢂ4
polyamide (100 g) changing polarity of the eluent (H O/
2
1
090, DAD detector (HP 1040), column, Lichrospher
RP-18 (5 ı
), 250ꢁ4 mm I.D. (Merck), flow rate, 0.8 ml/
min, mobile phase, A (MeCN) + B (H O containing
MeOH) in a stepwise mode, from 9:1 to 100% MeOH.
RB (0.4 g, H O/MeOH, 6:4) rechromatographed on
polyamide, H O/MeOH, 9:1–100% MeOH, to yield
2
`
2
2
2
1
isocratic modes: 98–90% B, 0–5 min, 90% B, 5–18 min,
% 0.1 N H PO ), elution, combination of gradient and
gentiobioside 8 (19 mg, H O/MeOH, 8:2), and prime-
2
3
4
veroside 4 (27 mg, H O/MeOH, 3:7). RB (90 mg,
2
3
9
2
0–85% B, 18–20 min, 85% B, 20–25 min, 85–70% B,
5–30 min, 70–30% B, 30–40 min, 30–0% B, 40–50 min.
H O/MeOH, 2:8) yielded, after the repeated CC on
2
polyamide and filtration through Sephadex LH-20
(MeOH), additional quantity of 4 (5 mg). RB (110
Preparative medium pressure chromatography (MPLC),
Lobar column (silica gel Si 60, size A or B). Dry-column
flash chromatography (DCFC), Silica gel Si 60; MN
Polyamide DC 6. TLC, 0.2 mm, silica gel 60 F 254
Merck, detection, under UV or by heating after spray-
ing with 50% H SO . Column chromatography (CC),
4
mg) was supended in MeOH, the insoluble fraction
(mostly 7) was filtered off, solute evaporated to dryness
and crystallized from CH Cl –MeOH to yield 9 (33
2
2
mg).
2
4
polyamide-6-powder (polycaprolactam); Sephadex
LH-20. Elemental C,H-analysis, combustion (Pregl)
method.
3.3.2. Aerial parts
The same extraction procedure as above (2ꢁ150 ml
MeOH) was applied on air dried aerial parts (42 g) to
obtain oily dark green residue (H, 11 g). Successive
3
.2. Plant material
extraction (3ꢁ60 ml) with Et O, EtOAc and n-BuOH of
2
H suspended in H O (80 ml) gave fractions HE (1.2 g),
2
Plant material was collected at the locality Ivanko-
HA (0.08 g) and HB (3.5 g), respectively. After eva-
poration of the water layer the residue HW (6.5 g) was
obtained. HE (1.2 g) was divided into six fractions
vica, Stara Planina (1850 m) in October 1999. A voucher
specimen (No. 11673) has been deposited in the herbar-
ium at the Faculty of Biology, Botanical Garden ‘‘Jev-
removac’’, Belgrade.
(HE1 ) by DCFC on silica gel using toluene/EtOAc
ꢂ6
(9.5:0.5–7:3). HE (toluene/EtOAc, 8:2) was identified as
3

N. Menkovi c´ et al. / Phytochemistry 61 (2002) 415–420
419
3 (35 mg). HE (77 mg), eluted with toluene/EtOAc, 7:3
yielded 1 (28 mg), upon crystallization from MeOH.
References
6
DCFC on polyamide (H O/MeOH, 7:3–100% MeOH–
2
Basnet, P., Kadota, S., Shimizu, M., Namba, T., 1994. Bellidifolin a
potent hypogycemic agent in streptozotocin (STZ)-induced diabetic
rats from Swertia japonica. Planta Med. 60, 507–511.
MeOH/CH Cl , 3:2) of HB (2.3 g) afforded HB (1.9 g,
2
2
1
H O/MeOH, 7:3–100% MeOH) and HB (0.24 g,
2
2
MeOH/CH Cl , 3:2). Crystallization from MeOH of
2
Bellmann, G., Jacot-Guillarmod, A., 1973. Contribution a
chimie du genre Gentiana. I) Etude de composes flavoniques et
xanthoniques dans les feuilles de Gentiana. lutea L. (1ere communi-
cation). Helvetica Chimica Acta 56, 284–294.
Correa, D.B., Fonseca e Silva, L.G., Gottlieb, O.R., Gonc
970. Quinone and xanthone constituents of Kielmeyera rupestris.
Phytochemistry 9, 447–451.
`
la phyto-
2
´
HB , followed by purification of the crystalline material
2
`
on Sephadex LH 20 (MeOH), yielded 5 (20 mg). Eva-
poration of supernatant of HB and purification of the
2
ˆ
¸ alves, S.J.,
residue (150 mg) on Sephadex LH 20 (MeOH) afforded
a fraction (45 mg) containing 11 as the major con-
stituent. Purification of an aliquot (15 mg) by PTLC
1
Gottlieb, O.R., Mesquita, A.A.L., de Oliveira, G.G., Teixeira de
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(
silica gel), EtOAc/MeOH/H O, 21:4:3 (three develop-
2
ments), followed by filtration through Sephadex LH-20,
yielded 11 (3.2 mg).
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1
591.
1
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Compound 9 was peracetylated with Ac O in pyridine
2
at room temp. overnight. The H NMR spectral data
of this acetate were identical to those of peracetylated
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`
thones dans les feuilles de Gentiana bavarica L. Helvetica Chimica
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1
Ishimaru, K., Sudo, H., Satake, M., Matsunaga, Y., Hasegawa, Y.,
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norswertianin-1-O-b-d-glucoside (Hostettmann et al.,
1
974).
3
(
.4. 1-O-Primeverosyl-3,8-dihydroxy-5-methoxyxanthone
4)
Jovanovic-Dunjic, R., 1973. Swertia L. In: Josifovic, M. (Ed.), Flore
´ ´ ´
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´ ´
Yellow crystals, mp 207–209 C, [ꢁ]d20=ꢂ68.75 (c
ꢃ
Red Book of Flora of Serbia 1. Extinct and Critically Endangered
Taxa. Ministry of Environment of the Republic of Serbia, Faculty
of Biology, University of Belgrade, Institution for Protection of
Nature of the Republic of Serbia, pp. 261–263.
0
.08, DMSO); UV: see Table 1; IR (KBr): ꢂ =3439,
max
13
ꢂ1
1
1
see Table 2; ESIMS m/z : 569 [M+H] , 591
636, 1401, 1262, 1106, 1083 cm ; H and C NMR:
+
M+Na]+ and 607 [M+K] . Elemental analysis
+
Kaldas, M., Hostettmann, K., Jacot-Guillarmod, A., 1974. Contri-
[
bution a
poses flavoniques et xanthoniques dans les feuilles de Gentiana
campestris L. (1ere communication). Helvetica Chimica Acta 57,
79–280.
Menkovic, N., Savikin-Fodulovic
`
la phytochimie du genre Gentiana. IX) Etude de com-
(
Found: C, 52.91; H, 5.05. C H O requires: C,
25 28 15
´
5
2.80; H, 4.97%).
`
2
ˇ
´
´
, K., Savin, K., 2000. Chemical
3
(
.5. 1-O-Gentiobiosyl-3,7-dimethoxy-8-hydroxyxanthone
8)
composition and seasonal variations in the amount of secondary
compounds in Gentiana lutea leaves and flowers. Planta Medica 66,
1
78–180.
Yellow crystals, mp 184–186 C; [a]d20=ꢂ33.63 (c
.33, DMSO); UV: see Table 1; IR (KBr): ꢂmax=3428,
650 sh, 1619, 1583, 1498, 1459, 1401, 1285, 1249, 1083
ꢃ
Miana, G.A., El-Hazimi, H.M.G., 1984. Xanthones of Centaurium
pulchellum. Phytochemistry 23, 1637–1638.
0
1
Neerja, P., Jain, D.C., Bhakuni, R.S., 2000. Phytochemicals from
genus Swertia and their biological activities. Indian Journal of
Chemistry 39B, 565–586.
cm ; 1H and 13C NMR: see Table 2; ESIMS m/z: 613
M+H]+ and 635 [M+Na] . Elemental analysis
ꢂ1
+
[
Otsuka, H., 1999. Triptexanthosides A-E: xanthone glycosides from
aerial parts of Tripterospermum japonicum. Chem. Pharm. Bull. 47,
962–965.
(
H, 5.27%).
Found: C, 53.02; H, 5.33. C H O requires: C, 52.93;
27 32 16
Peres, M., Tanus, J.N., Fernando, de O., F., 2000. Tetraoxygenated
naturally occurring xanthones. Phytochemistry 55, 683–710.
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thones de Gentiana Kochiana, Swertia decussata et S. perennis
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´ ´ ´
The authors are grateful to Professor V. Stevanovic,
´
´
´
Faculty of Biology, University of Belgrade for identifi-
cation of the plant material. The authors from Yugo-
slavia also acknowledge their gratitude to Ministry for
Science, Technologies and Development for financial
support.
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