Flavonoid glycosides and other constituents of Psorospermum androsaemifolium Baker (Clusiaceae)

Article abstract of DOI:10.1248/cpb.56.1428

Two new flavonoid glycosides, namely 3′-(2″,4″- dihydroxybenzyloxy)acanthophorin B (1b) and β,2,3′,4,4′,6- hexahydroxy-α-(α-L-rhamnopyranosyl)dihydrochalcone (2) were isolated from the leaves of Psorospermum androsaemifolium together with quercetin (1), a

Full text of DOI:10.1248/cpb.56.1428

1428
Chem. Pharm. Bull. 56(10) 1428—1430 (2008)
Vol. 56, No. 10
Flavonoid Glycosides and Other Constituents of Psorospermum
androsaemifolium BAKER (Clusiaceae)
Herve Martial Poumale POUMALE, ,a Rivoarison RANDRIANASOLO,b,d Jeannot Victor RAKOTOARIMANGA,c
*
Amelie RAHARISOLOLALAO,c Hans Christoph KREBS,b Jean Claude TCHOUANKEU,a and
a
Bonaventure Tchaleu NGADJUI
a Department of Organic Chemistry, Faculty of Science, University of Yaounde I; P.O. Box 812, Yaounde, Cameroon:
b Institut für Lebensmitteltoxikologie und Chemische Analytik, Chemische Analytik und Endokrinologie, Stiftung
Tierärztliche Hochschule; Bischofsholer Damm 15/123, D-30173 Hannover, Germany: c Department of Physical
Chemistry, Faculty of Science, University of Antananarivo; and d Department of Organic Chemistry, Faculty of Science,
University of Antananarivo; P.O. Box 906, Antananarivo 101, Madagascar.
Received April 28, 2008; accepted June 18, 2008; published online July 3, 2008
Two new flavonoid glycosides, namely 3ꢀ-(2ꢁ,4ꢁ-dihydroxybenzyloxy)acanthophorin B (1b) and b,2,3ꢀ,4,4ꢀ,6-
hexahydroxy-a-(a-L-rhamnopyranosyl)dihydrochalcone (2) were isolated from the leaves of Psorospermum an-
drosaemifolium together with quercetin (1), acanthophorin B (1a), a- (3) and b-amyrine (3a), vismiaquinone (4),
12-hentriacontanol and hentriacontane. The structures of these secondary metabolites were established using de-
tailed spectroscopic analysis and by comparison with published data. Compounds 1, 1a, 1b, 2, 3, 3a and 4 showed
weak antifungal and antibacterial activities.
Key words Psorospermum androsaemifolium; quercetin; dihydrochalcone; antimicrobial
Psorospermum androsaemifolium BAKER, an endemic phy on silica gel using a hexane/ethyl acetate gradient of in-
plant from Madagascar, locally known as “Tsifady”, creasing polarity; fractions A—C were obtained. Repeated
“Harongampanihy”, “Fanerana” or “Hazomafaika” belongs column chromatography and preparative TLC afforded
to the Clusiaceae family.1) In the traditional medicine it is quercetin (1), acanthophorin B (1a), vismiaquinone, a-
used as remedy for spiders or scorpions bite and also healing and b-amyrine, 12-hentriacontanol, hentriacontane and two
stomach disease.2,3) The widespread use of P. androsaemi- new flavonoid glycosides: 3ꢀ-(2ꢁ,4ꢁ-dihydroxybenzyloxy)-
folium in indigenous medicine for different ailments, justified acanthophorin B (1b) and b,2,3ꢀ,4,4ꢀ,6-hexahydroxy-a-(a-
1
further attempts to isolate and identify active compounds. L-rhamnopyranosyl)dihydrochalcone (2). The H- and 13C-
The present paper deals with the isolation and structural elu- NMR, and MS data of the known compounds were consistent
cidation of one new flavone glycoside and one new dihy- with those reported in the literature.
drochalcone glycoside including their antimicrobial activi-
Compounds 1 and 1a were isolated as yellow powder in
ties. To the best of our knowledge, no previous phytochemi- silica gel column (3ꢂ40 cm) from fraction A eluted with sol-
cal study has been reported on P. androsaemifolium.
vent system dichloromethane/methanol of increasing polar-
ity. The EI mass spectrum of compound 1a exhibited a mo-
Results and Discussion
lecular ion at m/z 448 corresponding to a molecular formula
1
The leaves of P. androsaemifolium were extracted at room C21H20O11. The H-NMR of 1a exhibited an ABX system at
temperature with methanol for 2 d. This extract was concen- d 8.30 (1H, d, Jꢃ8.4 Hz), 7.96 (1H, dd, Jꢃ8.4, 2.1 Hz) and
trated to dryness under vacuum, and after flash chromatogra- 7.21 (1H, d, Jꢃ2.0 Hz), a doublet of doublet at d 6.62 and
6.60 with Jꢃ2.3 Hz were characteristic of meta coupling pro-
tons for A ring of quercetin/acanthophorin B.4) The signals at
∗ To whom correspondence should be addressed. e-mail: poumale@yahoo.fr
© 2008 Pharmaceutical Society of Japan

October 2008
1429
Fig. 1. Selected HMBC Correlations in Compound 1b
Fig. 2. Selected HMBC Correlations in Compound 2
d 1.03 and between d 4.50—3.32 assigned to the rhamnopy-
ranosyl residue and the signal at d 5.42 was assigned to the (Jꢃ5.1 Hz), respectively whose chemical shifts and coupling
anomeric proton. These data were carried out in AntiBase5) patterns indicated the presence of –CO–CH(O–)–CH(OH)–
and the compound 1a was easily identified as acanthophorin group.8) The a-L-rhamnosyl unit was detected at d 5.34
1
B (1a) or quercetin-3-O-a-L-fucopyranoside. The H- and (Jꢃ3.1 Hz).9) In the aromatic region, an AB system at d 5.91
13C-NMR spectra of compounds 1 and 1a were nearly super- and 5.89 (d, Jꢃ2.6 Hz) and one ABX system at d 6.95 (1H,
imposable. The only significant difference being the absence d, Jꢃ8.0 Hz), 6.80 (1H, d, Jꢃ2.0 Hz) and 6.78 (1H, dd,
of the peaks of rhamnopyranosyl-residue moiety in com- Jꢃ8.0, 2.0 Hz) were observed. In the HMBC spectrum
pound 1.
(Fig. 2), correlations between the H-a signal and carbons 1,
Compound 1b was isolated as yellow powder in fraction B 1ꢀ, 1ꢀꢀ and CꢃO, between the H-b signal and carbons 2ꢀ, 6ꢀ
and showed on ESI-HR-MS an [MꢄH]ꢄ peak corresponding and CꢃO, between the H-1ꢀꢀ and carbons 2ꢀꢀ, 5ꢀꢀ and
to the molecular formula C27H25O13. The 13C/attached proton C-a as well as the close similarity with the shifts of
test (APT) NMR spectrum showed 27 carbon signals consis- a,b,2ꢀ,3,4,4ꢀ,5,6ꢀ-octahydroxydihydrochalcone10) indicated
tent with one methyl, thirteen methine and thirteen quater- that compound 2 was b,2,3ꢀ,4,4ꢀ,6-hexahydroxy-a-(a-L-
nary carbon signals.
rhamnopyranosyl)dihydrochalcone, which is described here
The H-NMR spectrum exhibited signals of one methyl for the first time.
The acetylation of 1b afforded compounds 1c and 5. Their
1
group as doublet at d 0.95 (d) and the multiplets between d
1
3.40 and 4.24 were characteristic of rhamnopyranosyl-sugar structures were confirmed by EI, ESI-HR-MS, IR and H-
ring.6) The anomeric proton appeared as doublet at d 5.40 and 13C-NMR spectra (see Experimental).
(Jꢃ3.4 Hz), implying the a-configuration of the rhamnose.7)
The antifungal and antibacterial activities of all the com-
In the aromatic region, an AB system at d 6.39 and 6.21 (d, pounds isolated from this plant were determined using the
Jꢃ1.6 Hz) was observed and two ABX system with the first agar diffusion method with 6 mm paper disks loaded with
one at d 7.42 (1H, dd, Jꢃ8.1, 2.2 Hz), 7.41 (1H, d, 40 mg of each compound. Compounds 1, 1a and 1b showed
Jꢃ2.2 Hz) and 6.78 (1H, d, Jꢃ8.0 Hz) and the second at d activities against Bacillus subtilis (11, 13, 14 mm inhibition
7.33 (1H, d, Jꢃ7.8 Hz), 7.29 (1H, dd, Jꢃ7.8, 1.9 Hz) and diameter), Staphylococcus aureus (12, 17, 15 mm), Strepto-
6.91 (1H, d, Jꢃ1.9 Hz) were also observed. The comparison myces viridochromogenes (Tü 57) (15, 16, 20 mm), and
of this data with compound 1a showed an additional 2,4-di- Escherichia coli (12, 10, 11 mm), respectively. b,2,3ꢀ,4,4ꢀ,6-
hydroxybenzene which was connected at the position 3ꢀ of Hexahydroxy-a-(a-L-rhamnopyranosyl)dihydrochalcone (2)
acanthophorin B according to the HMBC correlation (Fig. showed weak activities against Mucor miehi (13 mm), and
1). The peak at m/z 109 in EI-MS also supported the pres- Escherichia coli (11 mm). Vismiaquinone (4) was weakly ac-
ence of this moiety. The analysis of all these data compared tive against Candida albicans (14 mm) and hentriacontane
to those of acanthophorin B led to the conclusion that com- was weakly active against Staphylococcus aureus (13 mm).
pound 1b was 3ꢀ-(2ꢁ,4ꢁ-dihydroxybenzyloxy)acanthophorin a- (3) and b-Amyrine (3a) showed weak activity against
B or 3ꢀ-(2ꢁ,4ꢁ-dihydroxybenzyloxy)quercetin-3-O-a-L-fuco- Bacillus subtilis (12, 13 mm) and Candida albicans (14,
pyranoside isolated and described here for the first time.
Compound 2 was isolated as yellow powder in fraction C
eluted with hexane/ethyl acetate (5 : 2). The (ꢄ)-ESI-HR
mass spectrum indicated a pseudomolecular ion [MꢄH]ꢄ at
m/z 469.40921, corresponding to the molecular formula
C21H25O12. Comparison of the spectral data of compounds 1a
and 2 indicated the same sugar moiety, which was confirmed
by the peak at m/z 321 [MꢅC6H11O4]ꢄ. The IR spectrum of
compound 2 revealed a broad signal at n 3415 cmꢅ1 indicat-
ing free hydroxyl group, and an ester absorptions at n 1724
(CꢃO) and 1247 (C–O) cmꢅ1.
11 mm), respectively.
Experimental
Materials and Methods NMR spectra were measured on Varian Unity
300 (300.145 MHz) and Varian Inova 500 (499.876 MHz) spectrometers.
ESI mass spectra were recorded on a Finnigan LCQ with quaternary pump
Rheos 4000 (Flux Instrument). ESI HR mass spectra were recorded on a
Bruker FTICR 4.7 T mass spectrometer. EI mass spectra were recorded on a
Finnigan MAT 95 spectrometer (70 eV) with perfluorkerosene as a reference
substance for HR-EI-MS. IR spectra were recorded on a Perkin-Elmer 1600
Series FT-IR spectrometer from films. Flash chromatography was carried out
on silica gel (230—400 mesh). Rf values were measured on Polygram SIL
G/UV254 (Macherey-Nagel & Co.) and melting and decomposition points
were measured with the melting point apparatus of Electrothermal and were
not corrected.
Plant Material The leaves of Psorospermum androsaemifolium BAKER
were collected in April 2005 in the eastern rain forest of Madagascar. The
plant was authenticated at the botanical and zoological park of Tsimbazaza
Antananarivo Madagascar where a voucher specimen is deposited.
Hydrolysis Experiments Acid hydrolysis of 1b (4.0 mg) was per-
formed using 1% aq. HCl at 95 °C for 120 min and usual workup afforded
The 13C/APT NMR spectrum showed 21 carbon signals, of
which one was assigned to methyl, twelve to methine and
1
eight to quaternary carbon signals. The H-NMR spectrum
exhibited signals of one broad doublet of three protons at d
1.19 and the multiplets between d 3.30 and 3.70 are charac-
teristic of a rhamnopyranosyl residue.6) The a and b protons
of dihydrochalcone appeared as doublets at d 5.09 and 4.58 quercetin (1, 1.5 mg) and rhamnose (1 mg). For rhamnose detection, the final

1430
Vol. 56, No. 10
aqueous acidic mixture was extracted with mixture of ethyl acetate, then the
aqueous layer was neutralized for determination of the released sugar moiety
using silica gel plates with EtOAc–H2O (3 : 1), giving Rf value of 0.7.
Anisaldehyde/sulphuric acid was employed as a spray for colour (brown) de-
tection of the rhamnose-sugar.
CD3OD) d: 6.43 (1H, d, Jꢃ2.1 Hz, H-2), 6.78 (1H, dd, Jꢃ8.5, 2.1 Hz, H-6),
7.41 (1H, t, Jꢃ8.5 Hz, H-5), 7.42 (1H, dd, Jꢃ8.5, 2.1 Hz, H-4). 13C-NMR
(100 MHz, CD3OD) d: 159.7 (s, C-1, C-3), 136.3 (d, C-6), 110.5 (d, C-4, C-
6), 104.2 (d, C-2). EI-MS m/z (%): 110 ([M]ꢄ, 100), 94 (56), 79 (23), 56
(15), 43 (17).
Extraction and Isolation Air dried powdered leaves of Psorospermum
androsaemifolium (400 g) was extracted with MeOH at room temperature
during 48 h. After removing the solvent by evaporation under reduced pres-
sure, the crude extract (67 g) was chromatographed on silica gel using
hexane/ethyl acetate in increasing polarity. A total of three main fractions
[A—C] were collected and evaluated for their antimicrobial activity in vitro.
All these fractions showed no antimicrobial activity.
Fraction A (5.0 g) eluted with CH2Cl2–MeOH in increasing polarity using
PTLC and Sephadex LH-20 for purification yielded quercetin (1, 2.7 mg),11)
acanthophorin B (1a, 13.4 mg) and vismiaquinone (4, 15.0 mg).12)
Fraction B (13.0 g) was chromatographed on silica gel and eluted with a
mixture of hexane/ethyl acetate in increasing polarity to yield 3ꢀ-(2ꢁ,4ꢁ-dihy-
droxybenzyloxy)acanthophorin B (1b, 20.3 mg), a- (3, 7.1 mg) and b-
amyrine (3a, 3.4 mg).13)
Fraction C (17.0 g) was chromatographed on silica gel and eluted using
hexane/ethyl acetate. A total of 35 fractions (of ca. 300 ml each) were
collected and combined on the basis of TLC analysis leading to two main
series I—II. Series I (4 g) [fractions 1—16] was eluted with a mixture of
hexane/ethyl acetate (5 : 2) to deliver b,2,3ꢀ,4,4ꢀ,6-hexahydroxy-a-(a-L-
rhamnopyranosyl)dihydrochalcone (2, 2.4 mg). Series II (1.5 g) [fractions
17—35] was column chromatographed on silica gel and eluted with
CH2Cl2–MeOH (3 : 1) to yield 12-hentriacontanol (1.9 mg)14) and hentria-
contane (4.7 mg).15)
b,2,3ꢀ,4,4ꢀ,6-Hexahydroxy-a-(a-L-rhamnopyranosyl)dihydrochalcone
(2) Yellow powder. mp 150—152 °C. Rfꢃ0.52 (hexane/25% ethyl acetate).
1H-NMR (400 MHz, CD3OD) d: 6.95 (1H, d, Jꢃ8.0 Hz, H-5ꢀ), 6.80 (1H, d,
Jꢃ2.0 Hz, H-2ꢀ), 6.78 (1H, dd, Jꢃ8.0, 2.0 Hz, H-6ꢀ), 5.91 (1H, d, Jꢃ2.6 Hz,
H-5), 5.89 (1H, d, Jꢃ2.6 Hz, H-3), 5.34 (1H, d, Jꢃ3.1 Hz, H-1ꢁ), 5.09 (1H,
d, Jꢃ5.1 Hz, H-a), 4.58 (1H, d, Jꢃ5.1 Hz, H-b), 3.65 (1H, dd, Jꢃ3.0,
1.5 Hz, H-2ꢁ), 3.55 (1H, dd, Jꢃ8.8, 1.5 Hz, H-3ꢁ), 3.40 (1H, dd, Jꢃ8.8,
5.0 Hz, H-4ꢁ), 3.35 (1H, m, H-5ꢁ), 1.19 (3H, br d, H-6ꢁ). 13C-NMR
(100 MHz, CD3OD) d: 196.0 (s, CꢃO), 168.7 (s, C-4), 165.5 (s, C-2), 164.1
(s, C-6), 147.4 (s, C-4ꢀ), 146.7 (s, C-3ꢀ), 129.2 (s, C-1ꢀ), 120.5 (d, C-6ꢀ),
116.3 (d, C-5ꢀ), 115.5 (d, C-2ꢀ), 102.6 (s, C-1), 102.2 (d, C-1ꢁ), 97.7 (d, C-3),
96.3 (d, C-5), 84.0 (d, C-b), 78.6 (d, C-a), 73.8 (d, C-5ꢁ), 71.2 (d, C-4ꢁ), 71.1
(d, C-3ꢁ), 70.5 (d, C-2ꢁ), 17.9 (q, C-6ꢁ). IR (film) cmꢅ1: 3415, 2943, 2466,
1724, 1639, 1622, 1575, 1462, 1463, 1394, 1326, 1247, 1159, 1118, 1096,
1075, 996, 888, 719, 677. (ꢄ)-ESI HR-MS m/z: 469.40921 ([MꢄH]ꢄ, Calcd
469.40954 for C21H25O12). EI-MS m/z (%): 468 ([M]ꢄ, 17), 436 (12), 410
(15), 290 (78), 274 (13), 256 (22), 210 (30), 188 (9), 148 (10), 119 (16), 109
(7), 96 (26), 86 (12), 58 (17), 44 (31). [a]D27 ꢅ17.4 (cꢃ0.18, MeOH).
Antimicrobial Assay Agar diffusion tests were performed in the usual
manner16) with Bacillus subtilis and Escherichia coli (on peptone agar),
Staphylococcus aureus (Bacto nutrient broth), Streptomyces viridochromo-
genes (M test agar), the fungi Mucor miehei and Candida albicans
(Sabouraud agar), and three microalgae (Chlorella vulgaris, Chlorella
sorokiniana and Scenedesmus subspicatus).
3ꢀ-(2ꢁ,4ꢁ-Dihydroxybenzyloxy)acanthophorin B or 3ꢀ-(2ꢁ,4ꢁ-Dihydroxy-
benzyloxy)quercetin-3-O-a-L-fucopyranoside (1b) Yellow powder. mp
The test substances were dissolved in chloroform/methanol (87 : 13)
azeotrope and paper disks (f 6 mm) were impregnated with each 40 mg pro
disk using a 100 ml syringe, dried for 1 h under sterile conditions and placed
on the pre-made agar test plates. Plates with bacteria and fungi were kept in
an incubator at 37 °C for 12 h, micro algae plates were kept for 3 d at room
temperature in a day light incubator. The diameter of inhibition zones was
measured.
141—143 °C. Rfꢃ0.31 (hexane/25% ethyl acetate). 1H-NMR (400 MHz,
CD3OD) d: 7.42 (1H, dd, Jꢃ8.1, 2.2 Hz, H-6ꢀ), 7.41 (1H, d, Jꢃ2.2 Hz, H-
2ꢀ), 7.33 (1H, d, Jꢃ7.8 Hz, H-6ꢆ), 7.29 (1H, dd, Jꢃ7.8, 1.9 Hz, H-5ꢆ), 6.91
(1H, d, Jꢃ1.9 Hz, H-3ꢆ), 6.78 (1H, d, Jꢃ8.0 Hz, H-5ꢀ), 6.39 (1H, d,
Jꢃ1.6 Hz, H-8), 6.21 (1H, d, Jꢃ1.6 Hz, H-6), 5.40 (1H, d, Jꢃ3.4 Hz, H-1ꢁ),
4.24 (1H, dd, Jꢃ3.3, 1.5 Hz, H-2ꢁ), 3.75 (1H, dd, Jꢃ9.3, 1.5 Hz, H-3ꢁ), 3.43
(1H, m, H-5ꢁ), 3.33 (1H, dd, Jꢃ9.3, 5.7 Hz, H-4ꢁ), 0.95 (1H, d, Jꢃ5.6 Hz,
H-6ꢁ). 13C-NMR (100 MHz, CD3OD) d: 179.7 (s, C-4), 164.9 (s, C-7), 163.3
(s, C-5), 159.4 (s, C-2), 158.6 (s, C-9), 151.4 (s, C-4ꢆ), 149.8 (s, C-4ꢀ),
146.6 (s, C-1ꢆ), 146.5 (s, C-3ꢀ), 146.1 (s, C-2ꢆ), 136.3 (s, C-3), 123.9 (d, C-
5ꢆ), 123.0 (d, C-6ꢀ), 122.9 (s, C-1ꢀ), 117.8 (d, C-3ꢆ), 117.0 (d, C-2ꢀ), 116.4
(d, C-5ꢀ), 115.8 (d, C-6ꢆ), 105.9 (s, C-10), 103.6 (d, C-1ꢁ), 99.8 (d, C-6),
94.8 (d, C-8), 73.3 (d, C-5ꢁ), 72.1 (d, C-3ꢁ), 72.0 (d, C-4ꢁ), 71.9 (d, C-2ꢁ),
17.7 (q, C-6ꢁ). IR (film) cmꢅ1: 3440, 2924, 2366, 1693, 1651, 1602, 1565,
1504, 1462, 1436, 1394, 1356, 1289, 1275, 1195, 1118, 1086, 1059, 994,
887, 813, 750, 719, 670. (ꢄ)-ESI HR-MS m/z: 557.47196 ([MꢄH]ꢄ, Calcd
557.47187 for C27H25O13). EI MS m/z (%): 556 (Mꢄ, 9), 447 (15), 426 (9),
218 (100), 203 (33), 189 (22), 161 (10), 146 (13), 135 (19), 119 (16), 109
(18), 97 (26), 83 (37), 69 (40), 57 (42). [a]D27 ꢅ23 (cꢃ0.9, MeOH).
Acknowledgements The authors are grateful to the financial support of
D.A.A.D (Deutscher Akademischer Austauschdienst) research grant and to
the Organic Chemistry Institute of the University of Hanover for IR, EIMS
and NMR spectra.
References
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2ꢁ,3ꢁ,4ꢁ,5-Tetraacetoxyacanthophorin
B or 2ꢁ,3ꢁ,4ꢁ,5-Tetraacetoxy-
quercetin-3-O-a-L-fucopyranoside (1c) 3ꢀ-(2ꢁ,4ꢁ-Dihydroxybenzyloxy)-
acanthophorin B (1b, 7 mg) was dissolved in pyridine (1 ml) and acetanhy-
dride (1 ml). The solution was stirred for 5 h at 70 °C. Hydrolysis and usual
work-up gave 5 (1.5 mg, 4%) and 1c (3 mg, 47%) as an yellow solid. Melting
point: 136—138 °C. Rfꢃ0.48 (hexane/25% ethyl acetate). 1H-NMR
(400 MHz, CD3OD) d: 7.30 (1H, d, Jꢃ2.5 Hz, H-2ꢀ), 7.32 (1H, dd, Jꢃ8.5,
2.5 Hz, H-6ꢀ), 6.95 (1H, d, Jꢃ8.5 Hz, H-5ꢀ), 6.40 (1H, d, Jꢃ2.5 Hz, H-8),
6.21 (1H, d, Jꢃ2.5 Hz, H-6 ), 5.62 (1H, d, Jꢃ3.0 Hz, H-1ꢁ), 5.50 (1H, dd,
Jꢃ3.1, 1.9 Hz, H-2ꢁ), 5.28 (1H, dd, Jꢃ9.6, 1.8 Hz, H-3ꢁ), 4.29 (1H, dd,
Jꢃ9.6, 5.3 Hz, H-4ꢁ), 3.42 (1H, m, H-5ꢁ), 2.15 (3H, s, Ac-5), 2.05 (3H, s,
Ac-4ꢁ), 2.01 (3H, s, Ac-3ꢁ), 1.95 (3H, s, Ac-2ꢁ), 0.89 (3H, d, Jꢃ5.3 Hz, H-
6ꢁ). 13C-NMR (100 MHz, CD3OD) d: 178.1 (s, C-4), 170.6 (s, CꢃO, Ac-5),
170.5 (s, CꢃO, Ac-2ꢁ), 170.4 (s, CꢃO, Ac-4ꢁ),170.2 (s, CꢃO, Ac-3ꢁ), 165.1
(s, C-7), 162.1 (s, C-5), 158.5 (s, C-2), 157.7 (s, C-9), 149.0 (s, C-4ꢀ),146.0
(s, C-3ꢀ), 134.0 (s, C-3), 122.2 (d, C-6ꢀ), 121.9 (s, C-1ꢀ), 115.6 (d, C-2ꢀ),
115.5 (d, C-5ꢀ), 104.9 (s, C-10), 99.0 (d, C-1ꢁ), 98.0 (d, C-8), 93.9 (d, C-6),
70.5 (d, C-5ꢁ), 69.5 (d, C-4ꢁ), 69.3 (d, C-3ꢁ), 68.7 (d, C-2ꢁ), 20.1 (q, CH3-5),
19.5 (q, CH3-2ꢁ, 3ꢁ, 4ꢁ), 16.6 (q, CH3-6ꢁ). IR (film) cmꢅ1: 3363, 1743, 1652,
1603, 1501, 1442, 1365, 1199, 1164, 1801, 1043, 965, 809, 785, 642. (ꢄ)-
ESI HR-MS m/z: 617.41021 ([MꢄH]ꢄ, Calcd 617.41074 for C29H29O15). EI-
MS m/z (%): 616 ([M]ꢄ, 30), 574 (44), 490 (10), 302 (100), 286 (13), 268
(12), 263 (29), 194 (21), 178 (9), 143 (15), 124 (8), 110 (14), 94 (23), 79
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1,3-Dihydroxybenzene (5) Yellow powder. 1H-NMR (400 MHz,