Synthesis of Glycosides with 4-(4-Hydroxyphenyl)-1,2,3-thia- and -selenadiazole Aglycones

Article abstract of DOI:10.1134/S1070363219070089

Glycosylation of 4-(4-hydroxyphenyl)-1,2,3-thia(selena)diazoles with 1-α-bromo-2,3,4,6-tetra-O-acetyl-D-glucopyranose, 1-α-bromo-2,3,4,6-tetra-O-acetyl-D-galactopyranose, and 1-α-bromo-2,3,5-tri-O-acetyl-D-xylopyranose under the conditions of interphase catalysis has afforded the corresponding acetylated glycosides. An alternative pathway of selenadiasole glycosides synthesis from semicarbazones of 1-β-O-(4-acetylphenyl)-2,3,4,6-tetra-O-acetyl-D-glucopyranose, -2,3,4,6-tetra-O-acetyl-D-galactopyranose, and -2,3,5-tri-O-acetyl-D-xylopyranose via oxidation with selenium dioxide has been elaborated.

Full text of DOI:10.1134/S1070363219070089

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 7, pp. 1398–1405. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Obshchei Khimii, 2019, Vol. 89, No. 7, pp. 1038–1046.
Synthesis of Glycosides with 4-(4-Hydroxyphenyl)-1,2,3-thia-
and -selenadiazole Aglycones
L. M. Pevznera*, M. L. Petrova, E. B. Erkhituevab, V. A. Polukeevc, and A. V. Stepakovb
a St. Petersburg State Institute of Technology (Technical University), Moskovskii pr. 26, St. Petersburg, 190013 Russia
*e-mail: pevzner_lm@list.ru
b St. Petersburg State University, St. Petersburg, Russia
c Institute of Experimental Medicine, St. Petersburg, Russia
Received December 13, 2018; revised December 13, 2018; accepted December 20, 2018
Abstract—Glycosylation of 4-(4-hydroxyphenyl)-1,2,3-thia(selena)diazoles with 1-α-bromo-2,3,4,6-tetra-O-
acetyl-D-glucopyranose, 1-α-bromo-2,3,4,6-tetra-O-acetyl-D-galactopyranose, and 1-α-bromo-2,3,5-tri-O-acetyl-D-
xylopyranose under the conditions of interphase catalysis has afforded the corresponding acetylated glycosides.An
alternative pathway of selenadiasole glycosides synthesis from semicarbazones of 1-β-O-(4-acetylphenyl)-2,3,4,6-
tetra-O-acetyl-D-glucopyranose, -2,3,4,6-tetra-O-acetyl-D-galactopyranose, and -2,3,5-tri-O-acetyl-D-xylopyranose
via oxidation with selenium dioxide has been elaborated.
Keywords: glycosylation, Könnigs–Knorr reaction, interphase catalysis, 1,2,3-thiadiazoles, semicarbazides,
1,2,3-selenadiazoles
DOI: 10.1134/S1070363219070089
Targeted delivery of synthetic drugs has remained a
topical issue. Low bioavailability of certain drugs de-
mands their high concentration to achieve the therapeutic
effect, which leads to negative side effects. This problem
can be resolved by exploiting the natural delivery path-
ways involved in metabolism. Carbohydrates metabo-
lism is among them, providing delivery of mono- and
oligosaccharides and various glycosides including O-
arylglycosides into the cells. We have suggested taking
advantage of this pathway to enhance bioavailability of
4-(4-hydroxyphenyl)-1,2,3-thia(selena)diazoles which
exhibit antiviral [1], antimicrobial [2], and fungicide
[2] activity. Prediction of biological activity by means
of PASS software [3] has shown that O-glucosides, O-
galactosides, and O-Xylosides with such aglycones may
exhibit the inhibiting effect towards glycerophospho-
transferase, affect the penetrability of cell membranes,
act as antagonists of anaphylatoxin receptors, and show
antineoplastic action with probability >0.7. They can be
also used for the treatment of restenosis. On the contrary,
probability of antimicrobial and fungicide action of these
compounds has been estimated as of 0.6. Therefore, the
glycosides may demonstrate wider range of biological
activity as compared to free aglycones. Hence, devel-
opment of the protocols for preparation of the marked
compound is an important task.
The interphase-catalytic variant of the Könnigs–
Knorr reaction is a convenient method for preparation
of phenylglycosides [4, 5]. The process is carried out
in a water–chloroform medium using excess of phenol
and sodium or potassium hydroxide (as 1.0–1.25 M.
solution) with respect to acetylhalogenose. We used that
protocol for glycosylation of 4-(4-hydroxyphenyl)-1,2,3-
thia(selena)diazoles.
The reaction of 4-(4-hydroxyphenyl)-1,2,3-thiadiazole
with 1-α-bromo-2,3,4,6-tetra-O-acetyl-D-glucopyranose
1, 1-α-bromo-2,3,4,6-tetra-O-acetyl-D-galactopyranose
2, or 1-α-bromo-2,3,4-tri-O-acetyl-D-xylopyranose 3
was carried out according to the standard procedure at
the halogenose : thiadiazole : triethylbenzylammonium
bromide : potassium hydroxide molar ratio of 1 :2 : 0.8 :
2.2 in a water-chloroform system at 55°C during 8 h.
Since 1,2,3-thiadiazole derivatives were sensitive to the
action of bases, potassium hydroxide was used as 0.6 M
solution, which significantly increased the yield of the
target product as compared to the reactions at higher al-
kali concentration [4, 5]. After separation of the reaction
1398

SYNTHESIS OF GLYCOSIDES WITH 4-(4-HYDROXYPHENYL)-1,2,3-THIA-
1399
Scheme 1.
AcO
OAc
O
Y
O
Y
X
X
Z
O
TEBA-Br, KOH
N
OAc
AcO
AcO
+
HO
HO
CHCl3ꢀH2O
N
N
N
OAc
Z
Br
4, 5, 7, 8
1, 2
O
O
OAc
AcO
AcO
AcO
Z
TEBA-Br, KOH
N
O
OAc
+
CHCl3ꢀH2O
N
N
N
OAc
Z
Br
6, 9
3
X = OAc, Y = H (1); X = H, Y = OAc (2); X = OAc, Y = H, Z = S (4), Se (7); X = H, Y = OAc, Z = S (5), Se (8); Z = S (6), Se (9).
mixtures and crystallization from ethanol, glycosides
4-6 were obtained in 26, 45, and 41% yield, respectively
(Scheme 1). The presence of 1,2,3-thiadiazole ring in the
products was confirmed by the presence of the thiadiazole
ring proton signal at 8.5–8.6 ppm in the 1H NMR spectra
and of the carbon nuclei signals at 129.2 (C5-thiadiazole)
and 157.3–157.6 ppm (C4-thiadiazole) in the 13C NMR
spectra.
formation of 4-hydroxyacetophenone glycoside, obtain-
ing of its semicarbazone, and oxidation of the latter into
1,2,3-selenadiazole. The major problem of such pathway
was the selectivity of oxidation with selenium dioxide
because the carbohydrate fragment could be also involved
in the reaction.
Glucoside 10, galactoside 11, and xyloside 12 were
obtained via glycosylation of 4-hydroxyacetophenone
according to the procedure in [4]. Their reactions with
semicarbazide hydrochloride was carried out in ethanol
in presence of sodium acetate (glycoside : semicarbazide
hydrochloride : sodium acetate molar ratio 1 : 1.2 : 2.4,
refluxing for 8 h). Semicarbazones 13–15 were obtained
Structure of the obtained compounds was also con-
firmed by means of X-ray diffraction analysis data with
glycoside 6 as the example (see the figure).
The reaction of 4-(4-hydroxyphenyl)-1,2,3-selena-
diazole with halogenoses 1-3 was carried out similarly.
The selenadiazole ring turned out to be much more labile
under the reaction conditions: noticeable formation of
colloid selenium was observed. Glycosides 7–9 were
obtained in 15, 30, and 19% yield, respectively (Scheme
1). It is to be seen that the yield of galactoside 8 was sig-
nificantly higher as compared to glucoside 7 and xyloside
9, coinciding with the trend observed in [5] for other
phenols. The presence of selenadiazole ring in compounds
7–9 was confirmed by the proton signals at 9.3–9.4 ppm
(2JHSe = 40.4 Hz for satellites) and the carbon signals at
136 (C5) and 157 ppm (C4) in the NMR spectra.
1
in 78, 59, and 79% yield, respectively (Scheme 2). H
Low yield of the selenadiazole-based glycosides in-
spired us to use another pathway of their synthesis: the
formation of selenadiazole ring using the preliminarily
prepared glycoside. A standard procedure of selena-
diazoles synthesis is the oxidation of semicarbazones of
methyl ketones with selenium dioxide in acetic acid [6].
Therefore, we decided to adopt the protocol including
General view of 1-β-O-[4-(1,2,3-thiadiazol-4-yl)phenyl]-
2,3,4-tri-O-acetyl-D-xylopyranose 6 molecule in crystal
shown as thermal ellipsoids at 50% probability.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 7 2019

1400
PEVZNER et al.
Scheme 2.
O
AcO
AcO
O
O
O
H2NꢀNHCONH2·HCl
O
Y
X
Y
X
HN
N
NH2
CH3COONa
OAc
AcO
OAc
AcO
O
10, 11
13, 14
O
O
O
O
O
H2NꢀNHCONH2·HCl
HN
NH2
AcO
AcO
CH3COONa
AcO
AcO
OAc
N
OAc
O
12
15
X = OAc, Y = H (10, 13); X = H, Y = OAc (11, 14).
NMR spectra of the prepared compounds in DMSO-d6
contained the methyl group signal shifted upfield from
2.57 ppm in the ketone to 2.16–2.23 ppm and the signal of
the corresponding carbon atom was shifted from ~26 ppm
to ~14 ppm in the 13C NMR spectra. The carbonyl carbon
nucleus signal at ~197 ppm disappeared, and the signal
of the hydrazone carbon atom was observed at about
144 ppm. Besides that, the signal of the carbonyl carbon
atom of the amide fragment appeared at 157 ppm. The
protons of the NH2 and NH fragments gave broadened
signals at ~6.5 and 9.3 ppm, respectively.
crystallization from ethanol gave selenadiazole 7 in 17%
yield. The oxidation of galactoside 14 also led to the
formation of selenadiazole 8 in 28% yield. The oxida-
tion of xylozide 15 proceeded via two pathways giving
a mixture of selenadiazole 9 and ketone 12 in the 1 : 0.3
molar ratio. The yield of compounds 9 and 12 was 34 and
12%, respectively. We failed to separate that mixture by
crystallization.
Hence, it was shown that direct glycosylation of
4-(4-hydroxyphenyl)-1,2,3-thia- and -selenadiazoles was
possible. Besides, selenadiazole ring could be formed
via modification of aglycone directly in the glycoside,
though optimization of conditions for both processes
was required.
Oxidation of semicarbazones 13–15 with selenium
dioxide was carried out in acetic acid at 68–70°C for
4 h as described elsewhere [7], the semicarbazone :
selenium dioxide molar ratio was 1 :1.2. Separation of
the reaction mixture after oxidation of glucoside 13 and
The final stage of the synthesis was removal of the
acetyl protecting groups in the carbohydrate fragment.
Scheme 3.
AcO
HO
O
O
O
O
Y
X
Y
X
AcO
MeONa
MeOHꢀCHCl3
N
N
OH
HO
OAc
N
N
Z
4, 5, 7, 8
Z
16ꢀ19
O
O
O
O
HO
HO
MeONa
AcO
N
OH
N
OAc
AcO
MeOHꢀCHCl3
N
N
Z
Z
6, 9
20, 21
X = OAc, Y = H, Z = S (4), Se (7); X = H, Y= OAc, Z = S (5), Se (8); X = OH, Y = H, Z = S (16), Se (18); X = H, Y= OH, Z =
S (17), Se (19); Z = S (6, 20) Se (9, 21).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 7 2019

SYNTHESIS OF GLYCOSIDES WITH 4-(4-HYDROXYPHENYL)-1,2,3-THIA-
1401
Due to low solubility of glycosides 4–9 in methanol, the
reaction was carried out in the 2 : 1 methanol-chloroform
mixture in the presence of catalytic amounts of sodium
methylate. Despite high sensitivity of selenadiazole ring
to the action of strong bases, methanolysis proceeded
without noticeable appearance of colloid selenium. Crys-
tallization of free glycosides 16–21 from the reaction
mixture proceeded for 2–3 days.
8 h, washed with 0.6 N potassium hydroxide (2×9 mL),
then with 10 mL of water, with 10 mL of brine and dried
over calcium chloride. Chloroform was removed and
the residue crystallysed from ethanol.
1-β-O-[4-(1,2,3-Thiadiazol-4-yl)phenyl]-2,3,4,6-
tetra-O-acetyl-D-glucopyranose (4). Yield 26%, white
crystals, decomp. 215°C, [α]D20 –16.8 (c = 0.83, chloro-
form). 1H NMR spectrum (CDCl3), δ, ppm: 2.06 s (3Н,
СН3СО), 2.08 s (3Н, СН3СО), 2.10 s (3Н, СН3СО), 2.11 s
(3Н, СН3СО), 3.94 d. d. d [1Н, Н5-Glu, J(H6AH5) = 2.4 Hz,
J(H6ВH5) = 5.6 Hz, J(H4H5) = 10.0 Hz], 4.22 d. d [1Н,
Н6А-Glu, JАВ = 10.4 Hz, J(H6AH5) = 2.4 Hz], 4.33 d.
d [1Н, Н6В-Glu, JАВ = 10.4 Hz, J(H6ВH5) = 5.6 Hz],
5.19–5.23 m, 5.30–5.37 m (4Н, Н1–4-Glu), 7.14 d (2Н,
Н2,6-Ph, JНН = 8.8 Hz), 8.01 d (2Н, Н3,5-Ph, JНН = 8.8 Hz),
8.60 s (1Н, Н5-thiadiazole). 13С NMR spectrum (CDCl3),
δC, ppm: 20.16 (СН3), 20.63 (СН3), 20.67 (СН3), 20.73
(СН3), 61.95 (С6-Glu), 68.25 (С5-Glu), 71.15 (С4-Glu),
72.20 (С3-Glu), 72.67 (С2-Glu), 98.80 (С1-Glu), 117.47
(С2,6-Ph), 126.13 (С4-Ph), 128.81 (С3,5-Ph), 129.29 (С5-
thiadiazole), 157.57 (С4-thiadiazole), 162.16 (С1-phenyl),
169.31 (С=О), 169.42 (С=О), 170.23 (С=О), 170.56
(С=О). Mass spectrum: m/z 531.1036 [M + Na]+. Calcu-
lated for C22H24N2O10S: [M + Na]+ 531.1044.
Yield of compounds 16–21 significantly depended
on the nature of carbohydrate, while the influence of the
aglycone structure was minor. Glucosides 16 and 18 were
obtained in 34 and 41% yield, respectively, the yield of
galactosides 17 and 19 was 73 and 79%, and the yield of
xylosides 20 and 21 was 82 and 73%, respectively. The
obtained glycosides were stable crystalline water-soluble
substances which is especially convenient for testing them
as pro-drugs which are activated by hydrolases.
EXPERIMENTAL
1Н and 13С NMR spectra were registered using a
Bruker AVANCE-400 spectrometer (400.13 MHz and
100.16 MHz for 1Н and 13С, respectively). High-resolution
mass spectra were obtained using a Brucker MicrOTOF
instrument. Melting points were measured using a Boёtius
apparatus. Specific rotation angle was measured using an
Optical Activity LD AA-55 polarimeter in chloroform
and DMSO.
1-β-O-[4-(1,2,3-Thiadiazol-4-yl)phenyl]-2,3,4,6-
tetra-O-acetyl-D-galactopyranose (5). Yield 45%, white
crystals, mp 158°C, [α]D20 +8.6 (c = 1.13, chloroform). 1H
NMR spectrum (CDCl3), δ, ppm: 2.04 s (3Н, СН3СО),
2.09 s (3Н, СН3СО), 2.11 s (3Н, СН3СО), 2.21 s (3Н,
СН3СО), 4.14 d. d. d [1Н, Н5-Gal, J(H6AH5) = 6.0 Hz,
J(H6ВH5) = Hz, J(H4H5) = 0.8 Hz], 4.20 d. d [1Н, Н6А-Gal,
JАВ = 11.2 Hz, J(H6AH5) = 6.0 Hz), 4.27 d. d (1Н, Н6В-
Gal, JАВ = 11.2 Hz, J(H6ВH5) = 7.2 Hz], 5.16 d [1Н, Н4-
Gal, J(H3H4) = 8.0 Hz], 5.17 d. d [1Н, Н2-Gal, J(H2H3) =
10.4 Hz, J(H1H2) = 3.0 Hz], 5.50 br. d [1Н, Н1-Gal,
J(H1H2)=3.0Hz],5.54d.d[1Н,Н3-Gal,J(H2H3)=10.4Hz,
J(H3H4) = 8.0 Hz], 7.16 d (2Н, Н2,6-Ph, JНН = 8.8 Hz),
8.01 d (2Н, Н3,5-Ph, JНН = 8.8 Hz), 8.60 s (1Н, Н5-
thiadiazole). 13С NMR spectrum (CDCl3), δС, ppm: 20.60
(СН3), 20.67 (СН3), 20.70 (СН3), 20.76 (СН3), 61.41
(С6-Gal), 66.87 (С5-Gal), 68.60 (С3-Gal), 70.79, 71.21
(С2,4-Gal), 99.34 (С1-Gal), 117.42 (С2,6-Ph), 126.08 (С4-
Ph), 128.21 (С3,5-Ph), 129.28 (С5-thiadiazole), 157.65
(С4-thiadiazole), 162.18 (С1-Ph), 169.41 (С=О), 170.12
(С=О), 170.24 (С=О), 170.39 (С=О). Mass spectrum:
m/z 531.1062[M + Na]+. Calculated for C22H24N2O10S:
[M + Na]+ 531.1044.
X-ray structural analysis of compound 6. Mono-
crystals of glycosode 6 were obtained via slow evapora-
tion of its solution in an ethanol–chloroform–ethyl acetate
mixture at room temperature in air. X-ray diffraction
experiment was carried out using a Bruker APEX2 CCD
diffractometer with graphite monochromator, λ(CuKα) =
1.5418 Å. Crystals of compound 6 had orthorhombic syn-
gony. They were colorless, C19H20N2O8S, M = 0436.43,
a = 48.5414(14) Å, b = 7.1361(3) Å, c = 5.8921(2) Å,
Z = 4, dcalc = 1.420 g/cm3, V = 2041.00(13) Å, space
group P21212. 46857 reflections were measured, 4275
of them being independent (Rint = 0.0905, Rσ = 0.0292).
Complete crystallographic data for compound 6 were
deposited at the Cambridge Crystallographic Data Centre
(CCDC 1919454).
Glycozylationof4-(4-hydroxyphenyl)thia(selena)-
diazoles (general procedure). To the mixure of 4.9 nmol
of acetylhalogenose, 4.8 mmol of 4-(4-hydroxyphenyl)-
thia(selena)diazole, 3.9 mmol of TEBA-Br and 60 mL
of choroform 18 mL of 0.6 N potassium hydroxide was
added. The reaction mixture was stirred at 55°C for
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PEVZNER et al.
1-β-O-[4-(1,2,3-Thiadiazol-4-yl)phenyl]-2,3,5-tri-
5.50–5.58 m (4Н, Н1–4-Gal), 7.16 d (2Н, Н2,6-Ph, JНН
=
O-acetyl-D-xylopyranose (6). Yield 41%, white crystals,
decomp. 190–192°C, [α]D20 –40.7 (c = 1.09, chloroform).
1H NMR spectrum (CDCl3), δ, ppm: 2.11 s (3Н, СН3СО),
2.12s(6Н, СН3СО), 3.61d. d[1Н, Н5А-Xyl, JАВ =12.0Hz,
8.6 Hz), 8.02 d (2Н, Н3,5-Ph, JНН = 8.6 Hz], 9.34 s (1Н,
Н5-selenadiazole, satellite JНSe = 40.4 Hz). 13С NMR
spectrum (CDCl3), δС, ppm: 20.61 (СН3), 20.69 (СН3),
20.71 (СН3), 20.77 (СН3), 61.87 (С6-Gal), 66.87 (С5-
Gal), 68.62 (С3-Gal), 70.81, 71.20 (С2,4-Gal), 99.43 (С1-
Gal), 117.44 (С2,6-Ph), 127.40 (С4-Ph), 129.11 (С3,5-Ph),
136.17 (С5-selenadiazole), 157.25 (С4-selenadiazole),
162.26 (С1-Ph), 169.40 (С=О), 170.13 (С=О), 170.24
(С=О), 170.38 (С=О). Mass spectrum: m/z 579.0468 [M +
Na]+. Calculated for C22H24N2O10Sе: [M + Na]+ 579.0490.
J(H5AH4) = 7.4 Hz], 4.27 d. d [1Н, Н5В-Xyl, JАВ
=
12.0 Hz, J(H5BH4) = 4.6 Hz], 5.05 d. d. d [1Н, Н4-Xyl,
J(H5AH4) = 7.4 Hz, J(H5BH4) = 4.6 Hz, J(H3H4) = 7.4 Hz],
5.21–5.31 m (3Н, Н1–3-Xyl), 7.15 d (2Н, Н2,6-Ph, JНН
=
8.8 Hz), 8.01 d (2Н, Н3,5-Ph, JНН = 8.8 Hz), 8.59 s (1Н,
Н5-thiadiazole). 13С NMR spectrum (CDCl3), δС, ppm:
20.73 (СН3), 20.77 (СН3), 20.80 (СН3), 61.87 (С5-Xyl),
68.39 (С4-Xyl), 69.97 (С2-Xyl), 70.47 (С3-Xyl), 98.18
(С1-Xyl), 117.36 (С2,6-Ph), 125.86 (С4-Ph), 128.84 (С3,5-
Ph), 129.18 (С5-thiadiazole), 157.34 (С4-thiadiazole),
162.25 (С1-Ph), 169.40 (С=О), 169.85 (С=О), 169.91
(С=О). Mass spectrum: m/z 459.0847 [M + Na]+. Calcu-
lated for C19H20N2O8S: [M + Na]+ 459.0833.
1-β-O-[4-(1,2,3-Selenadiazol-4-yl)phenyl]-2,3,5-tri-
O-acetyl-D-xylopyranose (9). Yield 19%, grey crystals,
mp 172°C (decomp.), [α]D20 –24.7 (c = 0.87, chloroform).
1H NMR spectrum (CDCl3), δ, ppm: 2.11 s (3Н, СН3СО),
2.12s(6Н, СН3СО), 3.60d. d[1Н, Н5А-Xyl, JАВ =11.0Hz,
J(H5AH4) = 7.4 Hz], 4.28 d. d [1Н, Н5В-Xyl, JАВ
=
11.0 Hz, J(H5BH4) = 4.6 Hz], 5.05 d. d. d [1Н, Н4-Xyl,
J(H5AH4) = 7.4 Hz, J(H5BH4) = 4.8 Hz, J(H3H4) = 7.4 Hz],
1-β-O-[4-(1,2,3-Selenadiazol-4-yl)phenyl]-2,3,4,6-
tetra-O-acetyl-D-glucopyranose (7). Yield 15%, reddish
5.21–5.30 m (3Н, Н1–3-Xyl), 7.15 d (2Н, Н2,6-Ph, JНН
=
8.8 Hz), 8.02 d (2Н, Н3,5-Ph, JНН = 8.8 Hz), 9.32 s
(1Н, Н5-selenadiazole, satellite JНSe = 40.4 Hz). 13С
NMR spectrum (CDCl3), δС, ppm: 20.74 (СН3), 20.77
(СН3), 20.80 (СН3), 61.88 (С5-Xyl), 68.41 (С4-Xyl),
70.01 (С2-Xyl), 70.51 (С3-Xyl), 98.25 (С1-Xyl), 117.37
(С2,6-Ph), 127.17 (С4-Ph), 129.14 (С3,5-Ph), 136.10
(С5-selenadiazole), 156.92 (С4-selenadiazole), 162.32
(С1-Ph), 169.40 (С=О), 169.86 (С=О), 169.92 (С=О).
Mass spectrum: m/z 506.0280 [M + Na]+. Calculated for
C19H20N2O8Se: [M + Na]+ 507.0277.
20
crystals, mp 167°C (decomp.), [α]D –7.53 (c = 0.199,
chloroform). 1H NMR spectrum (CDCl3), δ, ppm: 2.07 s
(3Н, СН3СО), 2.08 s (3Н, СН3СО), 2.11 s (3Н, СН3СО),
2.12 s (3Н, СН3СО), 3.94 d. d. d [1Н, Н5-Glu, J(H6AH5) =
2.4Hz, J(H6ВH5)=5.4Hz, J(H4H5)=9.6Hz], 4.22d. d[1Н,
Н6А-Glu, JАВ = 12.4 Hz, J(H6AH5) = 2.4 Hz], 4.33 d. d [1Н,
Н6В-Glu, JАВ = 12.4 Hz, J(H6ВH5) = 5.4 Hz], 5.19–5.24
m, 5.31–5.38 m (4Н, Н1–4-Glu), 7.13 d (2Н, Н2,6-phenyl,
JНН = 8.8 Hz), 8.02 d (2Н, Н3,5-phenyl, JНН = 8.8 Hz),
9.33 s (1Н, Н5-selenadiazole, satellite JНSe = 40.4 Hz).
13С NMR spectrum (CDCl3), δС, ppm: 20.07 (СН3), 20.08
(СН3), 20.11 (СН3), 20.12 (СН3), 61.97 (С6-Glu), 68.26
(С5-Glu), 71.17 (С4-Glu), 72.20 (С3-Glu), 72.62 (С2-
Glu), 98.88 (С1-Glu), 117.50 (С2,6-Ph), 127.45 (С4-Ph),
129.11 (С3,5-Ph), 136.19 (С5-selenadiazole), 157.17 (С4-
selenadiazole), 162.24 (С1-Ph), 169.32 (С=О), 169.41
(С=О), 170.25 (С=О), 170.58 (С=О). Mass spectrum:
m/z 579.0477 [M + Na]+. Calculated for C22H24N2O10Sе:
[M + Na]+ 5791.0490.
Synthesis of glycoside semicarbazones 13-15
(general procedure). 6 mmol of semicarbazide hydro-
chloride and 12 mmol of sodium acetate were added
with stirring to a mixture of 5 mmol of glucoside 10,
galactoside 11, or xyloside 12 and 25 mL of ethanol.
The reaction mixture was refluxed with stirring and then
poured into 70 mL of water. The precipitate was filtered
off after several hours and dried in air.
1-β-O-(4-Acetylphenyl)-2,3,4,6-tetra-O-acetyl-D-
glucopyranose semicarbasone (13). Yield 78%, white
1-β-O-[4-(1,2,3-Selenadiazol-4-yl)phenyl]-2,3,4,6-
tetra-O-acetyl-D-galactopyranose (8). Yield 30%, pink
20
crystals, decomp. above 250°C, [α]D –1.8 (c = 0.274,
20
DMSO). 1H NMR spectrum (DMSO-d6), δ, ppm: 1.98 s
(3Н, СН3С=N), 2.02 s (6Н, СН3СО), 2.09 s (3Н, СН3СО),
2.16 s (3Н, СН3СО), 4.07 d (1Н, Н6А-Glu, JАВ = 11.6 Hz),
4.21 d. d [1Н, Н6В-Glu, JАВ = 11.6 Hz, J(H6ВH5) =
5.2 Hz]), 4.24–4.28 m [1Н, Н5-Glu, J(H6ВH5) = 5.2 Hz,
J(H4H5) = 9.6 Hz], 5.07 d. d [1Н, Н2-Glu, J(H1H2) =
7.8 Hz, J(H2H3) = 9.6 Hz], 5.23 m, 5.01 t, 5.45 t [2Н,
crystals, mp 148°C (decomp.), [α]D +18.2 (c = 0.43,
chloroform). 1H NMR spectrum (CDCl3), δ, ppm: 2.05 s
(3Н, СН3СО), 2.10 s (3Н, СН3СО), 2.11 s (3Н, СН3СО),
2.22 s (3Н, СН3СО), 4.14 br. d. d [1Н, Н5-Gal, J(H6AH5) =
6.2 Hz, J(H6ВH5) = 7.2 Hz], 4.21 d. d [1Н, Н6А-Gal,
JАВ = 11.2 Hz, J(H6AH5) = 6.2 Hz], 4.27 d. d [1Н, Н6В-
Gal, JАВ = 11.2 Hz, J(H6ВH5) = 7.2 Hz), 5.15–5.18 m,
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SYNTHESIS OF GLYCOSIDES WITH 4-(4-HYDROXYPHENYL)-1,2,3-THIA-
1403
Н3–4-Glu, J(H2H3) = J(H3H4) = J(H4H5) = 9.6 Hz], 5.62
d (1Н, Н1-Glu, J(H1H2) = 7.8 Hz), 6.46 br. s (2Н, NH2),
6.97 d (2Н, Н2,6-Ph, JНН = 8.8 Hz), 7.82 d (2Н, Н3,5-Ph,
JНН = 8.8 Hz), 9.25 s (1Н, NH). 13С NMR spectrum
(DMSO-d6), δС, ppm: 13.72 (СН3С=N), 20.77 (СН3),
20.82 (СН3), 20.87 (СН3), 20.98 (СН3), 62.09 (С6-Glu),
68.52 (С5-Glu), 71.19 (С4-Glu), 71.28 (С3-Glu), 72.39
(С2-Glu), 97.41 (С1-Glu), 116.38 (С2,6-Ph), 127.91 (С3,5-
Ph), 133.58 (С4-Ph), 143.94 (С=N), 157.04, 157.76 (С1-
Ph, С=О-amide), 169.59 (С=О), 169.79 (С=О), 170.08
(С=О), 170.47 (С=О). Mass spectrum: m/z 546.1685
[M + Na]+. Calculated for C23H29N3O11: [M + Na]+
546.1694.
169.94 (С=О). Mass spectrum: m/z 490.1213 [M + K]+.
Calculated for C20H25N3O9: [M + K]+ 490.1222.
Reaction of glucoside semicarbazones (13–15) with
selenium dioxide (general procedure). 6 mmol of finely
pulverized selenium dioxide was added to a suspension
of 5 mmol of semicarbazone in 15 mL of glacial acetic
acid. The reaction mixture was heated with stirring at
68–78°C for 4 h, cooled, and poured into 60 mL of water.
The obtained mixture was extracted with chloroform (3×
10 mL), washed with 10 mL of water, 10 mL of saturated
sodium bicarbonate solution, and 10 mL of brine, dried
over calcium chloride, filtered through silica gel layer, and
evaporated. The residue was crystallized from ethanol.
1-β-O-(4-Acetylphenyl)-2,3,4,6-tetra-O-acetyl-
D-galactopyranose semicarbasone (14). Yield 59%,
white crystals, decomp. above 250°C, [α]D20 +24.0 (c =
0.250, DMSO). 1H NMR spectrum (DMSO-d6), δ, ppm:
1.96 s (3Н, СН3С=N), 2.03 s (3Н, СН3СО), 2.05 s (3Н,
СН3СО), 2.16 s (6Н, СН3СО), 4.11 br. s (2Н, С6Н2-Gal),
4.46 br. s (1Н, Н5-Gal), 5.24–5.36 br. s (3Н, Н2–4-Gal),
5.53 d [1Н, Н1-Gal, J(H1H2) = 7.6 Hz], 6.48 br. s (2Н,
NH2), 6.97 d (2Н, Н2,6-Ph, JНН = 8.8 Hz), 7.82 d (2Н,
Н3,5-Ph, JНН = 8.8 Hz), 9.28 br. s (1Н, NH). 13С NMR
spectrum (DMSO-d6), δС, ppm: 13.74 (СН3С=N), 20.81
(СН3), 20.86 (СН3), 20.91 (СН3), 20.98 (СН3), 61.77
(С6-Gal), 67.71 (С5-Gal), 68.83 (С3-Gal), 70.60, 70.85
(С2,4-Gal), 98.03 (С1-Gal), 116.39 (С2,6-Ph), 127.93 (С3,5-
Ph), 133.56 (С4-Ph), 144.01 (С=N), 157.15, 157.81 (С1-
Ph, С=О-amide), 169.71 (С=О), 170.04 (С=О), 170.37
(С=О), 170.45 (С=О). Mass spectrum: m/z 546.1675 [M +
Na]+. Calculated for C23H29N3O11: [M + Na]+ 546.1694.
1-β-O-[4-(1,2,3-Selenadiazol-4-yl)phenyl]-2,3,4,6-
tetra-O-acetyl-D-glucopyranose (7). Yield 17%, pink
crystals, mp 164°C (decomp.). 1H and 13C NMR spectra
were identical to those described above.
1-β-O-[4-(1,2,3-Selenadiazol-4-yl)phenyl]-2,3,4,6-
tetra-O-acetyl-D-galactopyranose (8). Yield 28%,
pink crystals, mp 150°C. 1H and 13C NMR spectra were
identical to those described above.
1-β-O-[4-(1,2,3-Selenadiazol-4-yl)phenyl]-2,3,5-
tri-O-acetyl-D-xylopyranose (9) and 1-β-O-(4-
acetylphenyl)-2,3,5-tri-O-acetyl-D-xylopyranose (12).
Light grey powder. Compounds 9 and 12 was 1 : 0.3 (1H
NMR data), yield 34 and 12%, respectively. 1H and 13C
NMR spectra of compound 9 were identical to those
described above.
1-β-O-(4-Acetylphenyl)-2,3,5-tri-O-acetyl-D-
xylopyranose (12). 1HNMR spectrum (CDCl3), δ, ppm:
2.10 s (3Н, СН3СО), 2.11 s (3Н, СН3СО), 2.14 s (3Н,
СН3СО), 2.57 s (3Н, СН3-ketone), 3.60 d. d [1Н, Н5А-Xyl,
JАВ = 12.0 Hz, J(H5AH4) = 7.2 Hz], 4.24 d. d [1Н, Н5В-
Xyl, JАВ = 12.0 Hz, J(H5BH4) = 4.4 Hz], 5.02 d. d. d [1Н,
Н4-Xyl, J(H5AH4) = 7.2 Hz, J(H5BH4) = 4.4 Hz, J(H3H4) =
7.2 Hz], 5.19 d. d [1Н, Н2-Xyl, J(H1H2) = 5.6 Hz,
J(H2H3)=7.2Hz], 5.25d. d[1Н, Н3-Xyl, J(H2H3)=7.2Hz,
J(H3H4) = 7.2 Hz], 5.31 d (1Н, Н1-Xyl, J(H2H3) = 5.6 Hz),
7.05 d (2Н, Н2,6-Ph, JНН = 8.8 Hz), 7.95 d (2Н, Н3,5-Ph,
JНН = 8.8 Hz). 13С NMR spectrum (CDCl3), δС, ppm:
20.69 (СН3), 20.74 (СН3), 20.78 (СН3), 26.45 (СН3-
ketone), 61.77 (С5-Xyl), 68.21 (С4-Xyl), 69.67 (С2-Xyl),
70.16 (С3-Xyl), 97.53 (С1-Xyl), 116.16 (С2,6-Ph), 130.52
(С3,5-Ph), 132.19 (С4-Ph), 160.05 (С1-Ph), 169.32 (С=О),
169.81 (С=О), 196.97 (С=О-ketone).
1-β-O-(4-Acetylphenyl)-2,3,5-tri-O-acetyl-D-
xylopyranose semicarbasone (15). Yield 79%, white
crystals, decomp. above 250°C, [α]D20 +14.7 (c = 0.304,
1
DMSO). H NMR spectrum (DMSO-d6), δ, ppm: 2.11
s (6Н, СН3С=N, СН3СО), 2.13 s (3Н, СН3СО), 2.23 s
(3Н, СН3СО), 3.57 d. d [1Н, Н5А-Xyl, JАВ = 12.0 Hz,
J(H5AH4) = 7.4 Hz], 4.24 d. d [1Н, Н5В-Xyl, JАВ = 12.0 Hz,
J(H5BH4) = 4.6 Hz]), 5.03 d. d. d [1Н, Н4-Xyl, J(H5AH4) =
7.4 Hz, J(H5BH4) = 4.6 Hz, J(H3H4) = 7.4 Hz], 5.18–5.28
m (3Н, Н1–3-Xyl), 6.23 br. s (2Н, NH2), 7.02 d (2Н, Н2,6-
Ph, JНН = 8.8 Hz), 7.66 d (2Н, Н3,5-Ph, JНН = 8.8 Hz),
8.40 br. s (1Н, NH). 13С NMR spectrum (DMSO-d6), δС,
ppm: 13.27 (СН3С=N), 20.71 (СН3), 20.75 (СН3), 20.79
(СН3), 61.82 (С5-Xyl), 68.21 (С4-Xyl), 69.96 (С2-Xyl),
70.46 (С3-Xyl), 98.15 (С1-Xyl), 116.58 (С2,6-Ph), 127.47
(С3,5-Ph), 132.99 (С4-Ph), 145.45 (С=N), 157.23, 157.72
(С1-Ph, С=О-amide), 169.41 (С=О), 169.87 (С=О),
Methanolysis of glycoside acetates (general pro-
cedure). 20 mL of methanol and 6 drops of 1 M sodium
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1404
PEVZNER et al.
methylate solution in methanol were added to a solution of
5 mmol of glycoside acetate in 10 mLof chloroform. The
reaction mixture was left for 2 days at room temperature
(in the case of selenadiazole glycosides: in the dark). The
formed crystals were filtered off, washed with 3 mL of
methanol, and dried in air (for selenadiazole derivatives:
in the dark).
ppm: 3.25–3.29 m (2Н, Н2,3-Xyl), 3.35 d. d [1Н, Н5А-Xyl,
J(H5AH5B) = 10.4 Hz, J(H4H5A) = 10.4 Hz], 3.38–3.44 m
(1Н, Н4-Xyl), 3.78d. d[1Н, Н5В-Xyl, J(H5AH5B)=10.4Hz,
J(H4H5B) = 4.4 Hz], 4.99 d [1Н, Н1-Xyl, J(H1H2) = 6.8 Hz],
5.12 br. s (2Н, ОН), 5.38 br. s (1Н, ОН), 7.18 d (2Н, Н2,6-
Ph, J = 8.8 Hz), 8.08 d (2Н, Н3,5-Ph, J = 8.8 Hz), 9.50 s
(1Н, Н5- thiadiazole). 13С NMR spectrum (DMSO-d6),
δC, ppm: 66.22 (С5-Xyl), 69.82 (С4-Xyl), 73.54 (С2-Xyl),
76.90 (С3-Xyl), 101.11 (С1-Xyl), 117.31 (С2,6-Ph), 125.03
(С4-Ph), 128.92 (С3,5-Ph), 132.32 (С5- thiadiazole),
158.34 (С4-thiadiazole), 162.08 (С1-Ph).
1-β-O-[4-(1,2,3-Thiadiazol-4-yl)phenyl]-D-gluco-
pyranose (16). Yield 34%, white crystals, [α]D20 –37.7 (c =
0.83, DMSO). 1H NMR spectrum (DMSO-d6), δ, ppm:
3.16–3.22 m (1Н, Н2-Glu), 3.25–3.41 m (2Н, Н3,4-Glu),
3.39 d. d. d [1Н, Н5-Glu, J(H5H6A) = 6.0 Hz, J(H5H6B) =
1.2 Hz, J(H5H4) = 9.2 Hz], 3.49 d. d. d [1Н, Н6А-Glu,
J(H6AH6B) = 11.6 Hz, J(H5H6A) = 6.0 Hz, J(H6AOH) =
5.8 Hz]), 3.72 d. d. d [1Н, Н6В-Glu, J(H6AH6B) =
11.6 Hz, J(H5H6B) = 1.2 Hz, J(H6BOH) = 5.8 Hz]), 4.59 t
[1Н, СН2ОН, J(H6AOH)=J(H6BOH)=5.8Hz), 4.98d(1Н,
Н1-Glu, J(H1H2) = 7.2 Hz), 5.05 s (1Н, ОН, JHОH = 5.2 Hz),
1-β-O-[4-(1,2,3-Selenadiazol-4-yl)phenyl]-D-gluco-
20
pyranose (18). Yield 41%, grey powder, [α]D +208.3
(c = 0.708, DMSO). 1H NMR spectrum (DMSO-d6), δ,
ppm: 3.19 br. s (1Н, Н2-Glu), 3.29–3.41 m (3Н, Н3–5-Glu),
3.49br.d.d[1Н,Н6А-Glu,J(H6AH6B)=11.2Hz,J(H5H6A)=
5.4 Hz], 3.72 br. d. d [1Н, Н6В-Glu, J(H6AH6B) =
11.2 Hz, J(H5H6B) = 2.8 Hz]), 4.59 br. t (1Н, СН2ОН),
4.98 d [1Н, Н1-Glu, J(H1H2) = 6.8 Hz], 5.05 br. s (1Н,
ОН), 5.12 br. s (1Н, ОН), 5.37 br. s (1Н, ОН), 7.19 d (2Н,
Н2,6-Ph, J = 8.3 Hz), 8.08 d (2Н, Н3,5-Ph, J = 8.3 Hz),
10.09 s (1Н, Н5-selenadiazole, satellite JНSe = 41.2 Hz).
13С NMR spectrum (DMSO-d6), δC, ppm: 61.16 (С6-Glu),
70.17 (С5-Glu), 73.72 (С4-Glu), 77.09 (С3-Glu), 77.59
(С2-Glu), 100.69 (С1-Glu), 117.27 (С2,6-Ph), 126.31 (С4-
Ph), 129.13 (С3,5-Ph), 139.39 (С5-selenadiazole), 158.16
(С4- selenadiazole), 162.31 (С1-Ph). Mass spectrum:
m/z 411.0077 [M + Na]+. Calculated for C14H16N2O6Sе:
[M + Na]+ 411.0066.
5.12 d (1Н, ОН, JHОH = 4.8 Hz], 5.37 d (1Н, ОН, JHОH
=
4.8 Hz), 7.20 d (2Н, Н2,6-Ph, J = 8.8 Hz), 8.08 d (2Н,
Н3,5-Ph, J = 8.8 Hz), 9.52 s (1Н, Н5-thiadiazole). 13С
NMR spectrum (DMSO-d6), δС, ppm: 61.15 (С6-Glu),
70.17 (С5-Glu), 73.71 (С4-Glu), 77.08 (С3-Glu), 77.59
(С2-Glu), 100.62 (С1-Glu), 117.27 (С2,6-Ph), 124.91 (С4-
Ph), 128.88 (С3,5-Ph), 132.27 (С5-thiadiazole), 158.61
(С4-thiadiazole), 162.12 (С1-Ph). Mass spectrum: m/z
363.0620 [M + Na]+. Calculated for C14H16N2O6S: [M +
Na]+ 363.0621.
1-β-O-[4-(1,2,3-Thiadiazol-4-yl)phenyl]-D-galacto-
1-β-O-[4-(1,2,3-Selenadiazol-4-yl)phenyl]-D-galac-
topyranose (19). Yield 79%, pink powder, [α]D20 –13.3
20
pyranose (17). Yield 73%, white crystals, [α]D –14.4
1
(c = 0.656, DMSO). H NMR spectrum (DMSO-d6),
1
(c = 0.764, DMSO). H NMR spectrum (DMSO-d6),
δ, ppm: 3.43–3.48 m (1Н, Н3-Gal), 3.49–3.66 m (4Н,
Н2,5,6А,6В-Gal), 3.73 br. t (1Н, Н4-Gal), 4.54 d (1Н, ОН,
J = 4.8 Hz), 4.68 t {1Н, ОН, J[(ОН)Н6A,6B)] = 5.6 Hz},
4.89 d (1Н, ОН, J = 5.6 Hz), 4.94 d [1Н, Н1, J(H1H2) =
7.6 Hz]), 5.22 d (1Н, ОН, J = 5.2 Hz), 7.20 d (2Н, Н2,6-
Ph, J = 8.8 Hz), 8.08 d (2Н, Н3,5-Ph, J = 8.8 Hz), 9.51 s
(1Н, Н5-thiadiazole). 13С NMR spectrum (DMSO-d6),
δC, ppm: 60.86 (С6-Gal), 68.62 (С4-Gal), 70.74 (С3-Gal),
73.76 (С2-Gal), 76.07 (С5-Gal), 101.23 (С1-Gal), 117.29
(С2,6-Ph), 124.83 (С4-Ph), 128.88 (С3,5-Ph), 132.23 (С5-
thiadiazole), 158.67 (С4- thiadiazole), 162.14 (С1-Ph).
Mass spectrum: m/z 363.0630 [M + Na]+. Calculated for
C14H16N2O6S: [M + Na]+ 363.0621.
δ, ppm: 3.43–3.47 m (1Н, Н3-Gal), 3.49–3.65 m (4Н,
Н2,5,6А,6В-Gal), 3.73 br. s (1Н, Н4-Gal), 4.54 d (1Н, ОН,
J = 4.4 Hz), 4.68 t {1Н, ОН, J[(ОН)Н6A,6B)] = 5.6 Hz},
4.89 d (1Н, ОН, J = 5.6 Hz), 4.94 d [1Н, Н1-Gal, J(H1H2) =
7.6 Hz], 5.21 d (1Н, ОН, J = 5.2 Hz), 7.19 d (2Н, Н2,6-
Ph, J = 8.8 Hz), 8.08 d (2Н, Н3,5-Ph, J = 8.8 Hz), 10.09
s (1Н, Н5- selenadiazole, satellite JНSe = 39.6 Hz). 13С
NMR spectrum (DMSO-d6), δC, ppm: 60.86 (С6-Gal),
68.62 (С4-Gal), 70.62 (С3-Gal), 73.77 (С2-Gal), 76.06
(С5-Gal), 101.29 (С1-Gal), 117.29 (С2,6-Ph), 126.23 (С4-
Ph), 129.12 (С3,5-Ph), 139.35 (С5-selenadiazole), 158.24
(С4-selenadiazole), 162.35 (С1-Ph). Mass spectrum: m/z
411.0085 [M + Na]+. Calculated for C14H16N2O6Sе: [M +
Na]+ 411.0066.
1-β-O-[4-(1,2,3-Thiadiazol-4-yl)phenyl]-D-xylopy-
ranose (20). Yield 82%, light brown powder, [α]D20 -4.8
(c = 1.141, DMSO). 1H NMR spectrum (DMSO-d6), δ,
1-β-O-[4-(1,2,3-Selenadiazol-4-yl)phenyl]-D-xy-
20
lopyranose (21). Yield 73%, light brown powder, [α]D
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SYNTHESIS OF GLYCOSIDES WITH 4-(4-HYDROXYPHENYL)-1,2,3-THIA-
1405
1
+0.7 (c = 0.705, DMSO). H NMR spectrum (DMSO-
CONFLICT OF INTEREST
d6), δ, ppm: 3.25–3.31 m (2Н, Н2,3-Xyl), 3.50 d. d [1Н,
Н5А-Xyl, J(H5AH5B) = 10.6 Hz, J(H4H5A) = 10.4 Hz],
3.39–3.45 m (1Н, Н4-Xyl), 3.79 d. d [1Н, Н5В-Xyl,
J(H5AH5B) = 10.6 Hz, J(H4H5B) = 4.8 Hz], 4.99 d [1Н, Н1-
Xyl, J(H1H2) = 7.2 Hz], 5.10 d (1Н, ОН, JНН = 4.4 Hz),
5.16d(1Н,ОН,JНН =4.0Hz),5.40d(1Н,ОН,JНН =4.4Hz),
7.17 d (2Н, Н2,6-Ph, J = 8.8 Hz), 8.08 d (2Н, Н3,5-Ph, J =
No conflict of interest was declared by the authors.
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=
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(С3-Xyl), 101.18 (С1-Xyl), 117.32 (С2,6-Ph), 126.43 (С4-
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 7 2019