Fitoterapia 70 Ž1999.

148]151

New and rare flavonol glycosides from

leaves of Syzygium samarangense
A.G.R. Nair a,U , S. Krishnan a , C. Ravikrishnaa , K.P.
Madhusudanan b
a
Department of Chemistry, Pondicherry Uni¨ ersity, Pondicherry 605 014, India
b
Di¨ ision of Medicinal Chemistry, C.D.R.I, Lucknow 226 003, India

Received 25 August 1998; accepted 19 October 1998

Abstract

Two flavonol glycosides have been isolated and characterised from leaves of Syzygium
samarangense. One is the rare mearnsitrin (1) while the second, 29-C-methyl-59-O-gal-
loylmyricetin-3-O-a-L-rhamnopyranoside (2), is new. Detailed spectral data are provided for
both. Q 1999 Elsevier Science B.V. All rights reserved.

Keywords: Syzygium samarangense; Flavonols

1. Introduction

There is a growing interest in the analysis of new plants for flavonoid compounds
possessing a wide range of biological and pharmacological activities w1,2x. The
anti-inflammatory and antilipoperoxidative properties of a series of natural
flavonoids isolated from Indian and Spanish medicinal plants have been assessed
and encouraging results have been obtained w3,4x. Syzygium species are known for
their medicinal properties. Previous work revealed the presence of dimethoxymat-
teucinol in the fruits of S. samarangense w5x, 49,5-dihydroxy-7-methoxy-6,8-dimethyl

U
Corresponding author.

0367-326Xr99r$ - see front matter Q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 6 7 - 3 2 6 X Ž 9 9 . 0 0 0 1 3 - 1
 A.G.R. Nair et al. r Fitoterapia 70 (1999) 148]151 149

flavone and 49,5,7-trihydroxy-6,8-di-C-methyl flavone in S. alternifolium w6,7x,

myricetin-3-O-glucoside and myricetin-3-O-robinoside in S. cumini w8x. In continua-
tion of the search for new natural products from plants w9x, the leaves of Syzygium
samarangense ŽBlume. Merr. et L.M. Perry, syn. Eugenia ja¨ anica Lam. ŽMyrtaceae.
w10,11x were studied and the results leading to the isolation of flavonol glycosides 1
and 2 are presented.

2. Experimental

2.1. Plant material

S. samarangense leaves, collected from a 6-year-old plant growing in Pondicherry

on January 1995 and authenticated by Dr B. Kannabiran, School of Life Sciences,
Pondicherry University. A voucher specimen is kept in the Chemistry Department
of Pondicherry University, India.

2.2. Extraction and isolation

Fresh leaves Ž600 g. were extracted with 90% EtOH at reflux temperature. The
extract was concentrated, the dark green residue, separated on cooling, was
removed by filtration through cotton and the brown filtrate was partitioned with
benzene, Et 2 O, EtOAc and MEK. Preparative PC ŽWhatman No. 3, 15% AcOH,
descending, 5 h. of the solid from EtOAc fraction gave compound 1 ŽRf 0.61, 20
mg. and compound 2 ŽRf 0.51, 90 mg..

Mearnsitrin (1). Yellow needles, mp 180]1818C, w a x 28 D -148

ŽMeOH.; UVmax
ŽMeOH.: 265, 298sh, 338sh; ŽNaOMe.: 271, 328sh, 372; ŽNaOAc.: 272, 340sh;
ŽNaOAcrH 3 BO 3 .: 265, 305, 340sh; ŽAlCl 3 .: 274, 302, 340, 392sh; ŽAlCl 3rHCl.:
274, 302, 340, 392sh nm; 1 H-NMR Ž400 MHz, DMSO-d6 .: d 12.60 Ž1H, br s, 5-OH.,
9.25]9.75 Ž3H, br s, 7, 39,59-OH., 6.82 Ž2H, s, H-29, 69., 6.40 Ž1H, d, J 2 Hz, H-8.,
6.20 Ž1H, d, J 2Hz, H-6., 5.14 Ž1H, s, unresolved, Rh-H., 3.75 Ž3H, s, 49-OMe.,
4.00]3.00 Ž m, rhamnose protons., 0.82 Ž3H, d, J 6 Hz, Rh-CH 3 .; FABMS, positive,
m r z: 501 ŽM q Na, 78., 479 ŽM q H, 20., 333 Žaglycone q H, 20..

29-Methyl-59-O-galloylmyricetin-3-O-a-L-rhamnopyranoside (2). Yellow needles, mp

1928C Ždec., w a x 30
D -126 MeOH ; UVmax MeOH : 264, 300sh, 352; NaOMe : 264,
Ž . Ž . Ž .
327; ŽNaOAc.: 272, 316, 374; ŽNaOAcrH 3 BO 3 .: 262, 295sh, 374; ŽAlCl 3 .: 272, 308,
320, 418; ŽAlCl 3rHCl.: 272, 304sh, 363, 405sh nm; IR bands ŽKBr.: 3450, 2950,
1772, 1655 cmy1 ; 1 H-NMR Ž400 MHz, DMSO-d6 .: d 12.69 Ž1H, br s, 5-OH.,
9.07]9.24 Ž6H, br s, 7, 39, 49, 409, 590, 690-OH ., 6.85 Ž1H, s, H-69., 6.83 Ž2H, s,
390,790-H ., 6.49 Ž1H, d, J 2 Hz, H-8., 6.21 Ž1H, d, J 2 Hz, H-6., 5.25 Ž1H, s,
unresolved, Rh-H-1., 4.00]3.00 Ž m, rhamnose protons., 2.58 Ž3H, s, 29-CH 3 ., 0.84
Ž3H, d, J 6 Hz, Rh-CH 3 .; 13 C-NMR Ž100 MHz, DMSO-d6 .: 177.99 ŽC-4., 167.74
150 A.G.R. Nair et al. r Fitoterapia 70 (1999) 148]151

ŽC-109 ., 164.43 ŽC-7., 161.51 ŽC-5., 157.68 ŽC-9., 156.62 ŽC-2., 145.98 ŽC-409 ., 145.82
ŽC-609 ., 145.59 ŽC-39., 145.37 ŽC-49., 138.17 ŽC-509 ., 136.66 ŽC-59., 134.50 ŽC-3.,
120.72 ŽC-29., 119.87 ŽC-209 ., 119.54 ŽC-19., 108.97 ŽC-69., 108.17 ŽC-309 ., 108.17
ŽC-709 ., 104.25 ŽC-10., 102.12 ŽC-10 ., 98.91 ŽC-6. 93.76 ŽC-8., 71.62 ŽC-40 ., 70.75
ŽC-50 ., 70.50 ŽC-30 ., 70.23 ŽC-20 ., 20.69 Ž29-CH 3 ., 17.72 ŽC-60 ..

3. Results and discussion

Compound 1 was recognised as the rare flavonol mearnsitrin w12x by spectral

analysis. Compound 2 was purple under UV and yellow under UVrNH 3 indicating
a free 49-OH w13x. On acid hydrolysis, it yielded L-rhamnose, gallic acid and
monomethyl myricetin Žmol. wt. 332.. Mild alkaline hydrolysis ŽNaHCO3 . also gave
gallic acid, showing that it is linked as an ester. The presence of gallic acid was also
indicated by the enhanced UV absorbance of band II at 268 nm in MeOH
spectrum. The aglycone showed colour reactions typical of a 39,49,59-trihydroxy
system, and UV fluorescence and maxima similar to myricetin but different from
mearnsetin. The EIMS showed ions with characteristic m r z values expected for
A and C ring of myricetin w14x but different from B ring fragments. The 14 amu
increase in B ring fragment was attributed to C-methyl in B ring. This was also
supported by a characteristic peak at d 2.5 in 1 H-NMR and inverted signal at d
20.7 in the 13 C-ŽSEPT.-NMR spectra. The position of esterification by gallic acid
was fixed at 39 Žor 59. and not on 49 in the B ring by the presence of an o-dihydroxy
group revealed by the characteristic shift in AlCl 3 and AlCl 3rHCl spectra. A
careful analysis of the chemical shifts of the carbon atoms in the 13 C-NMR
spectrum of 2, its comparison with that of quercetin 3-O-a-L-rhamnopyranoside,
and application of substitution effects on carbon resonance by ]OHrO-galloyl
revealed the site of acylation at 59-OH and not at 39-OH. The position of
glycosylation was fixed at 3-OH by difference in UV fluorescence before and after
hydrolysis as well as by comparison with quercetin Ž59-deoxymyricetin.. The 13 C-
NMR spectrum of the glycoside was almost identical with that of quercetin
3-O-a-L-rhamnopyranoside in respect of A and C ring carbons. On this ground, the
structure of compound 2 was established as 29-C-methyl-59-O-galloylmyricetin-3-O-
a-L-rhamnopyranoside.

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