Chemistry of Natural Compounds, Vol. 41, No. 1, 2005
GLYCOSIDES AND THYMIDINE FROM
THE MOLLUSK Cryptochiton stelleri
I. I. Kapustina, T. N. Makar′eva,
UDC 547.918:593.96
A. I. Kalinovskii, and V. A. Stonik
In continuation of the search for biologically active compounds in marine organisms [1-3], we investigated the extract
of the mollusk
.
Cryptochiton stelleri
Mollusks were collected using a small trawl in September 1995 in the Sea of Japan near Tumannyi Cape (42° 58.90′
N, 134° 06.60′ E) at a depth of about 140 m. The ground specimens were extracted with ethanol. The alcohol was evaporated.
The aqueous solution was extracted with petroleum ether to remove nonpolar substances and left in a refrigerator overnight.
The precipitated salt was filtered off. The supernatant was concentrated in vacuum to give a polar fraction that was separated
over a column of silica gel L (40/100 µ, Czech Rep.) using a CHCl :ethanol gradient (50:1 → 5:1). The two most polar
3
fractions were purified over a column of Sephadex LH-20 using CHCl :ethanol (10:1) and then twice over silica gel with elution
3
byethylacetate:hexane (2:1 → 3.5:1) and (2:1 → 5:1). HPLC over a reversed-phase column (YMC-Pack ODS-A, 250 × 10 mm,
1.5 mL/min) using ethanol (60%) isolated three pure compounds (1-3).
-3
n-Butyl-α-D-glucopyranoside (1). Yield 4.2×10 % of the dry animal mass, R 0.20 (CHCl :ethanol:water,
f
3
11:3.5:0.2).
Ethyl-α-D-glucopyranoside (2). Yield 1.2×10 % ofthe dryanimal mass, R 0.47 (CHCl :ethanol:water, 11:3.5:0.2).
-3
f
3
The acetates of 1 and 2 (1a and 2a, respectively) were prepared by treating weighed portions of these compounds with
pyridine:acetic anhydride (1:1) for 1 d at room temperature. The solutions were evaporated to dryness with added benzene.
The structures of 1 and 2 were established using the modern NMR spectroscopy methods DEPT, COSY, and HMBC.
13
The proton spectra were interpreted using COSY experiments for 1a and 2a (Table 1). Signals for C atoms in C NMR spectra
of the sugars of 1 and 2 were assigned bycomparing them with those in spectra ofα-D-glucopyranoside [4]. Signals for C atoms
of the carbohydrates of 1a and 2a agree well with the corresponding values for the model acetate of α-D-glucopyranoside [5].
Therefore, both glycosides have the identical structure in the carbohydrate parts. Signals for C-2′, C-3′, and C-4′ of the aglycon
13
in the C NMR spectrum of 1 are similar to the corresponding signals of n-butanol [6].
-4
13
Thymidine (3). Yield 1.5×10 % of the dry animal mass. UV, PMR, and C NMR spectra of 3 agree with those of
standard thymidine and thymidine isolated by us previously from the sea pen Pavonaria finmarchica [3].
The chemical composition of the mollusk Cryptochiton stelleri has not previously been studied.
Pacific Institute of Bioorganic Chemistry, Far-East Division, Russian Academy of Sciences, 690022, Vladivostok, pr.
100-Letiya Vladivostoku, 159, fax (4232) 31 40 50, e-mail: piboc@stl.ru. Translated from Khimiya Prirodnykh Soedinenii,
No. 1, pp. 88-89, January-February, 2005. Original article submitted October 11, 2004.
0009-3130/05/4101-0109 ©2005 Springer Science+Business Media, Inc.
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Kapustina
