910
S.A.M. Hussein et al. / Phytochemistry 63 (2003) 905–911
alkaline hydrolysis (21 mg of 2 refluxed with 10 ml
aqueous 1 N NaOH, at 100 ꢁC, for 3h). Acidification of
the hydrolysate with aqueous 2 N HCl, followed by
extraction by ethyl acetate, washing of the organic layer
with water, filtration through anhydrous Na2SO4 and
Ellagic acid: Rf-values : Table ; UV lMmaexOH nm: Table 1;
ESI–MS: negative ion [M-H]ꢀ: m/z=301; 1H NMR 1H:
0
7.5 (s, H-3and H-3 ); Sanguisorbic acid: Rf-values :
Table ; UV l
MeOH
max
nm: Table 1; ESI–MS: negative ion
1
[M-H]ꢀ: m/z=469; H NMR: ꢀ ppm: 6.45 (d, J=2 Hz,
H-2), 7.02 (d, H=2 Hz, H-6), 7.5 (s, H-30). H NMR of
1
comparative paper chromatography proved the pre-
MeOH
max
sence of caffeic acid: Rf-values: Table 1; UV l
nm:
5: ꢀ ppm: Hexahydroxydipheoyl moieties: ꢀ ppm: 6.33,
6.39, (1 H in total, each s, H-30), 6.5, 6.55 (1 H in total,
each s, H-3); sanguisorboyl moiety: ꢀ ppm: 6.61, 6.63(1
H in total, each s, H-30), 7.03, 7.04 (1 H in total, d, J-2
Hz, H-6), 7.06, 7.09 (1 H in total, d, J=2 Hz, H-2); (a/
b)-glucose moieties: ꢀ ppm: 5.25 (d, J=2.5 Hz, H-1a),
4.83( d, J=8 Hz, H-1b), 5.05 (dd, J=8 Hz and 2 Hz, H-
2a), 4.66 (t, J=8 Hz, H-2b), 4.7–4.8 (m, H-3a, H-3b, H-
4a and H-4b), 4.18 (m, H-5a), 4.08 (m, H-5b), 5.52 (dd,
J=136 Hz, H-6 a), 5.50 (dd, J=13Hz and 6 Hz, H-6 b),
3.74 (d, J=12.5 Hz, H-6a), 3.70 (d, J=12.5, H-6b). 13C
NMR: Table 2.
Table 1; ESI:¼MS negative ion [M-z]ꢀ at m/z=179;
The remaining acidified hydrolysate was set acid free
through extraction with N,N-dimethyloctyl amine in
CHCl3 then concentrated in vacuo and examined by
comparative paper chromatography to prove the pre-
1
sence of xylose. H NMR of (2): ꢀ ppm: Caffeoyl moi-
ety: ꢀ ppm: 6.25 (1 H, d, J=16 Hz, H-70), 6.85 (1 H, d,
J=8 Hz, H-50), 7.0 (1 H, m, H-60), 7.04 (1 H, d, J=2.5
Hz, H-20), 7.60 (1 H, d, J=16 Hz, H-70); b-xylose moi-
ety: ꢀ ppm: 5.65 (d, J=7 Hz, H-1), 3,3-3.8 (m, over-
lapping other sugar and hydroxyl protons). 13C
chemical shifts: (Table 2).
3.5. 2,3-O-hexahydroxydiphenoyl-(ꢁ/ꢂ)-glucose (3)
Acknowledgements
MeOH
max
Rf-values: Table 1. UV l
nm: Table 1. ESI-MS
negative molecular ion [M-H]ꢀ: m/z=481. H NMR: ꢀ
ppm: Hexahydroxydipheoyl moiety: ꢀ ppm: 6.3, 6.31 (1
H in total, s, H-30), 6.42, 6.43(1 H in total, s, H-300); (a/b)-
glucose moieties: ꢀ ppm: 5.25 (1 H, d, J=2.5 Hz, H-1a),
4.88 (1 H, d, J=8 Hz, H-1b), 5.13(1 H, t, J=8 Hz, H-3a),
5.05 (1 H, t, J=8 Hz, H-3b), 4.81 (1 H, dd, J=8 Hz and
2.5 Hz, H-2a), 4.5 (1H, t, J=8 Hz, H-2b), 3.4–3.7 (m,
overlapping other sugar and hydroxyl protons).
The authors wish to express their deep gratitude to
Professor Dr. M. Linscheid, Institut fur Chemie, Hum-
boldt-University Berlin for the ESI-MS measurements.
1
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3.6. Bis-2,3;4,6-O-hexahydroxydiphenoyl-(ꢁ/ꢂ)-glucose,
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MeOH
max
Rf-values: Table 1. UV l
nm: Table 1. ESI–MS
1
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MeOH
max
Rf-values: Table 1. UV l
nm: Table 1. ESI–MS:
negative molecular ion [M-H]ꢀ: m/z=951. Acid hydro-
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h, yielded glucose, ellagic acid and sanguisorbic acid;
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ꢁ