Synthesis and molecular structure of new S-nucleosides of 5-(4-pyridyl)-4-aryl-4H-1,2,4-triazole-3-thiols

Article abstract of DOI:10.1002/jccs.200800124

The synthesis of some new S-nucleosides of 5-(4-pyridyl)-4-aryl-4H-l,2,4- triazole-3-thiols (4a-n) is described. Direct glycosylation of (4a-n) with tetra-O-acetyl-α-D-glucopyranosyl bromide in the presence of potassium hydroxide followed by deacetylation using dry ammonia in methanol gave the corresponding 3-S-(β-D-glucopyranosyl)-5-(4-pyridyl)-4-aryl-4H-l,2,4- triazoles (6a-n) in good yields. All the compounds were fully characterized by means of ¹H NMR, ¹³C NMR spectra and elemental analyses. To assist in the interpretation of the spectroscopic data, the crystal structure of 3-S-(2′,3′,4′,6′-tetra-O-acetyl-β-D- glucopyranosyl)-5-(4-pyridyl)-4-phenyl-4H-l,2,4-triazole (5a) was determined by X-ray diffraction.

Full text of DOI:10.1002/jccs.200800124

834
Journal of the Chinese Chemical Society, 2008, 55, 834-841
Synthesis and Molecular Structure of New S-nucleosides of
5-(4-Pyridyl)-4-aryl-4H-1,2,4-triazole-3-thiols
Huan-Huan Zhanga (
Gui-Fang Fanb (
), Xiu-Qin Hua* (
),
)
) and Peng-Fei Xua* (
aState Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. China
bJinchuan Group Limited, Jinchang, Gansu 737104, P. R. China
The synthesis of some new S-nucleosides of 5-(4-pyridyl)-4-aryl-4H-1,2,4-triazole-3-thiols (4a-n) is
described. Direct glycosylation of (4a-n) with tetra-O-acetyl-a-D-glucopyranosyl bromide in the pres-
ence of potassium hydroxide followed by deacetylation using dry ammonia in methanol gave the corre-
sponding 3-S-(b-D-glucopyranosyl)-5-(4-pyridyl)-4-aryl-4H-1,2,4-triazoles (6a-n) in good yields. All
the compounds were fully characterized by means of 1H NMR, 13C NMR spectra and elemental analyses.
To assist in the interpretation of the spectroscopic data, the crystal structure of 3-S-(2¢,3¢,4¢,6¢-tetra-O-
acetyl-b-D-glucopyranosyl)-5-(4-pyridyl)-4-phenyl-4H-1,2,4-triazole (5a) was determined by X-ray dif-
fraction.
Keywords: S-nucleosides; 1,2,4-Triazole; Glycosylation; Crystal structure.
INTRODUCTION
1,2,4-Triazole derivatives have a broad spectrum of
is given in Scheme I. 1-(4-Pyridyl)-4-aryl thiosemicarba-
zides (3a-n) were prepared by the condensation of 4-pyr-
idyl carboxylic acid hydrazide (1) with arylisothiocyanates
(2a-n) in good yields.33 The synthesis of 5-(4-pyridyl)-4-
aryl-4H-1,2,4-triazole-3-thiols (4a-n) was achieved by the
cyclization of 3a-n in the presence of sodium hydroxide.34
Each of the substituted 1,2,4-triazole-3-thiols (4a-n) was
subjected to coupling with 2,3,4,6-tetra-O-acetyl-a-D-glu-
copyranosyl bromide in the presence of potassium hydrox-
ide using ethanol as the solvent, and yields ranged from
48% to 89%. The subsequent procedure was the removal of
the protecting groups which could be easily achieved by
treatment of (5a-n) with ammonia gas in dry methanol. The
final desired S-nucleosides of 5-(4-pyridyl)-4-aryl-4H-
1,2,4-triazole-3-thiols (6a-n) were obtained successfully.
The yield of glycosylation was greatly influenced by aryl
substitution on the triazole ring. When the electron-donat-
ing groups were used, the yields could be greatly improved.
Furthermore, only the b-anomer was obtained as judged by
1H NMR, and the anomeric proton (H-1) was exhibited as a
doublet at d 5.51-5.62 (J1,2 = 9.0-10.8 Hz).
biological activities such as anti-inflammatory,1-5 antivi-
ral,6,7 anticonvulsant,8-10 antitumor,11-13 antidepressant,14
antifungal15-18 and antimicrobial activity.19-20 The applica-
tion of 1,2,4-triazoles is limited because of their poor solu-
bility in both organic solvents and water, so many modified
1,2,4-triazole derivatives have been reported in order to
improve their solubility and biological activities. Espe-
cially after the recognized biological properties of rib-
avirin,21 1-b-D-ribofuranosyl-1,2,4-triazole-3-carbox-
amide, the synthesis of N-nucleosides and C-nucleosides
as well as their acyclic analogues possessing a 1,2,4-tri-
azole moiety has attracted many workers22-24 in this field to
attempt to enhance the biological activity of these com-
pounds. During past decades, a great deal of modified N-
nucleosides25-27 and C-nucleosides28-31 have been greatly
emphasized, but only a few S-nucleosides have been re-
ported.32 In view of this, we turned our attention to the syn-
thesis of novel S-nucleosides of 1,2,4-triazole derivatives
from 5-(4-pyridyl)-4-aryl-4H-1,2,4-triazole-3-thiols and
tetra-O-acetyl-a-D-glucopyranosyl bromide.
The structures of 5a-n and 6a-n were confirmed by
1H NMR and 13C NMR, as well as by elemental analyses.
The 1H NMR spectrum for 5a-n showed four singlets in the
region of d 1.94-2.06 corresponding to four acetyl groups.
The multiplets at d 3.74-5.76 were attributed to seven pro-
tons of the sugar moiety. The aryl and pyridyl groups were
RESULTS AND DISCUSSION
Synthesis
The synthesis pathway leading to the title compounds
* Corresponding author. E-mail: xupf@lzu.edu.cn

Synthesis of Some New S-nucleosides
J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 835
Scheme I Synthesis of S-nucleosides of 5-(4-pyridyl)-4-aryl-4H-1,2,4-triazole-3-thiols (6a-n)
O
C
O
S
H H
C N N C NHR
EtOH, reflux
N
NHNH2
RNCS
+
N
2a-n
1
3a-n
N
N
tetra-O-acetyl-a-D-
N
R
SH
glucopyranosyl bromide
NaOH, reflux
KOH, EtOH
N
4a-n
OH
OAc
4
O
5
O
HO
HO
AcO
AcO
1
S
S
2
OH
3
OAc
N
N
N
NH3/CH3OH
N
N
R
N
R
N
N
6a-n
5a-n
R: a) Ph b) o-C2H5OPh c) p-C2H5OPh d) o-CH3OPh e) p-CH3OPh f) o-CH3Ph g) m-CH3Ph
h) p-CH3Ph i) o-BrPh j) m-BrPh k) p-BrPh l) o-ClPh m) m-ClPh n) p-ClPh
found in the region of d 6.95-8.60. The successful deacet-
ylation of 5a-n could be easily supported by the disappear-
ance of four sharp singlets around d 2.00 in the 1H NMR
spectrum of 6a-n.
ring show large deviations from the value of 120° usually
found in the trigonal planar arrangement, which is common
in five-membered rings.
The methyl H atoms were then constrained to an ideal
geometry, with C-H distances of 0.96 Å and Uiso(H) = 1.5
Ueq(C), but were allowed to rotate freely about their C-C
bond. All remaining H atoms were placed in geometrically
idealized positions and constrained to ride on their parent
Biological Activities
The anti-HIV-1 reverse transcriptase (RT), anti-HIV-
1 protease (PR) and HIV-1 integrase (IN) activities of these
kinds of compounds have been evaluated, but none of these
compounds showed obviously anti-HIV activity. Other bi-
ological activities are still under investigation.
Crystal Structure
The molecular structure of 5a is shown in Fig. 1. This
crystal was obtained by crystallization of 5a from ethanol.
The structure determination shows clearly that the acetyl-
glucose ring adopts 4C1 chair conformation with all sub-
stituents in equatorial positions. Furthermore, compound
5a is in the b-configuration and the C5-S1-C15 angle is
97.90 (11)°. The heterocyclic ring is planar within experi-
mental error. The endocyclic bond lengths N1-C15 and
N2-C16 of 1.307 (3) and 1.314 (3) Å, respectively, clearly
indicate they are double bonds. The C-N-N angles in the
Fig. 1. ORTEP drawing and atom labelling scheme of
the compound 5a with thermal ellipsoids drawn
at the 50% probability level.

836 J. Chin. Chem. Soc., Vol. 55, No. 4, 2008
Zhang et al.
atoms, with C-H distances in the range of 0.93-0.98 Å and
Uiso(H) = 1.2 Ueq(C).
Table 2. Selected bond lengths [Å] and angles [°] for 5a
S-C5
S-C15
O1-C1
O1-C5
O2-C2
O2-C10
O3-C3
O3-C8
O4-C4
O4-C6
O5-C6
O6-C8
O1-C1-C12
O1-C1-C2
O2-C2-C3
O2-C2-C1
O3-C3-C2
O3-C3-C4
O4-C4-C3
O4-C4-C5
O1-C5-C4
O1-C5-S1
C4-C5-S1
O5-C6-O4
O5-C6-C7
O4-C6-C7
O6-C8-O3
O6-C8-C9
O3-C8-C9
O9-C10-O2
O9-C10-C11
O2-C10-C11
O7-C12-C1
O8-C13-O7
O8-C13-C14
1.811 (2)
O7-C12
O7-C13
O8-C13
O9-C10
N1-C15
N2-C16
N3-C15
N3-C16
N3-C22
N4-C19
N4-C20
N1-N2
O7-C13-C14
N1-C15-N3
N1-C15-S1
N3-C15-S1
N2-C16-N3
N2-C16-C17
N3-C16-C17
N4-C19-C18
N4-C20-C21
C27-C22-N3
C23-C22-N3
C15-N1-N2
C16-N2-N1
C15-N3-C16
C15-N3-C22
C16-N3-C22
C19-N4-C20
C5-O1-C1
C10-O2-C2
C8-O3-C3
C6-O4-C4
C13-O7-C12
C15-S1-C5
1.432 (3)
1.336 (3)
1.206 (4)
1.188 (4)
1.307 (3)
1.314 (3)
1.370 (3)
1.376 (3)
1.442 (3)
1.300 (5)
1.328 (4)
1.385 (3)
111.9 (3)
CCDC 627631 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free
of charge via www.ccdc.cam.ac.uk/conts/retrieving.html
(or from the CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK; Fax: +44-1223-336033; E-mail: deposit@ccdc.cam.
ac.uk). A summary of the crystallographic data and details
of the structure refinements is listed in Table 1. Selected
bond lengths and angles are listed in Table 2.
1.751 (2)
1.432 (3)
1.423 (3)
1.447 (3)
1.370 (3)
1.445 (3)
1.367 (3)
1.442 (3)
1.365 (3)
1.187 (3)
1.188 (3)
106.63 (19)
108.30 (17)
106.58 (18)
109.56 (19)
106.79 (17)
109.89 (18)
109.89 (17)
105.20 (17)
108.98 (18)
107.83 (14)
110.15 (15)
122.7 (2)
127.6 (2)
109.8 (2)
124.2 (2)
125.4 (2)
110.4 (2)
CONCLUSIONS
111.2 (2)
In summary, we have successfully synthesized 14
new S-nucleosides of 5-(4-pyridyl)-4-aryl-4H-1,2,4-tri-
zoles-3-thiols (5a-n) via nucleophilic substitution reaction
and 14 of their deacetylation compounds 6a-n in accept-
able to good yields. The preliminary study indicates that
the solubility of these modified 1,2,4-triazole derivatives
was indeed improved.
127.17 (18)
121.67 (17)
109.9 (2)
122.5 (2)
127.5 (2)
125.8 (3)
124.3 (3)
119.1 (2)
118.7 (2)
106.84 (19)
107.84 (19)
104.21 (18)
126.11 (18)
129.67 (19)
115.4 (3)
111.47 (16)
117.9 (2)
117.75 (18)
117.41 (18)
116.6 (2)
97.90 (11)
EXPERIMENTAL SECTION
All reagents of analytical grade were used without
purification. All melting points were uncorrected and de-
123.7 (3)
125.5 (3)
110.7 (3)
108.11 (19)
121.1 (3)
126.8 (3)
Table 1. Crystal and structure refinement summary for
compound 5a
Formula
C27H28N4O9S
584.59
Formula weight
Crystal system
Space group
orthorhombic
P2(1)2(1)2(1)
a = 8.1215 (10)
b = 16.471 (2)
c = 22.119 (3)
a = b = g = 90°
2958.9(6)
Unit-cell dimensions (Å)
termined on a Yanaco MP micoscropic melting point appa-
ratus. Elemental analyses were carried out on a Vario E1
Elemental meter. 1H NMR spectrum were recorded at 300
MHz and 13C NMR spectrum were recorded at 75 MHz.
The X-ray diffractometer data was collected on a Bruker
SMART ApexCCD area detector with a graphite-mono-
chromated MoKa radiation (l = 0.71073 Å) at 294(2) K.
The crystal structure was solved by direct methods using
SHELXS-9735 and refined by full-matrix least-squares
methods on F2 using SHELXL-97.36 All H atoms were de-
termined from a difference Fourier map.
Unit-cell volume, V (Å3)
Formula per unit cell, Z
Dcalcd (g/cm3)
4
1.312
0.166
1224
Absorption coefficient, m (mm-1)
F(000)
Crystal size (mm)
Index ranges
0.30 ´ 0.30 ´ 0.25
-9 £ h £ 9
-17 £ k £ 19
-25 £ l £ 24
0.9518 and 0.9596
5203 (Rint = 0.0361)
5203/0/375
R1 = 0.0419, wR2 = 0.1178
R1 = 0.0454, wR2 = 0.1217
1.072
Max. and min. transmission
Independent reflections
Reflections/restraints/parameters
Final R indices [I > 2s(I)]
R indices (all data)
General Procedure for Preparation of S-Nucleoside
Derivatives of 1,2,4-Triazoles (5a-n)
Goodness-of-fit on F2
5-(4-Pyridyl)-4-aryl-4H-1,2,4-triazole-3-thiol (4a-n)

Synthesis of Some New S-nucleosides
J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 837
(2 mmol) was dissolved in the solution of KOH (2 mmol) in
ethanol (25 mL). After the mixture was stirred at room tem-
perature for 30 min, 2,3,4,6-tetra-O-acetyl-a-D-glucopyr-
anosyl bromide (2 mmol, 0.82 g) was added. The reaction
mixture was stirred at room temperature for 48 h. The mix-
ture was concentrated and washed with water. The crude
product was purified by flash column chromatography.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-phenyl-4H-1,2,4-triazole (5a)
Yield: 65%; Mp: 172-174 °C; [a] 2D0 +4 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 1.96-1.99 (m, 12H), 3.78-
3.82 (m, 1H), 4.07 (dd, J = 12.6 & 2.1 Hz, 1H), 4.21 (dd, J =
12.6 & 4.2 Hz, 1H), 5.04-5.11 (m, 2H), 5.25 (t, J = 9.3 Hz,
1H), 5.57 (d, J = 10.5 Hz, 1H), 7.20 (d, J = 7.2 Hz, 2H),
7.25 (d, J = 5.7 Hz, 2H), 7.47-7.56 (m, 3H), 8.50 (d, J = 5.7
Hz, 2H); 13C NMR (75 MHz, CDCl3) d 20.4, 20.6, 61.4,
67.7, 69.8, 73.6, 76.1, 83.8, 121.4, 127.2, 130.2, 130.6,
133.1, 133.7, 150.1, 150.5, 152.9, 169.3, 169.8, 170.4;
Anal. Calcd. for C27H28N4O9S: C, 55.47; H, 4.83; N, 9.58;
Found: C, 55.40; H, 4.47; N, 9.65.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-o-methoxyphenyl-4H-1,2,4-triazole (5d)
Yield: 80%; Mp: 84-86 °C; [a] 2D0 -11 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 1.99-2.03 (m, 12H), 3.63 (d,
J = 9.3 Hz, 3H), 3.75-3.82 (m, 1H), 4.02-4.10 (m, 1H),
4.20-4.30 (m, 1H), 5.03-5.14 (m, 2H), 5.22-5.30 (m, 1H),
5.53-5.58 (m, 1H), 7.01-7.09 (m, 2H), 7.14-7.23 (m, 1H),
7.31 (d, J = 5.7 Hz, 2H), 7.53 (t, J = 7.8 Hz, 1H), 8.54 (d, J =
5.7 Hz, 2H); 13C NMR (75 MHz, CDCl3) d 20.3, 55.4, 61.4,
67.6, 69.6, 73.4, 75.8, 83.6, 84.1, 112.3, 120.7, 121.2,
121.6, 128.3, 128.8, 132.1, 134.1, 149.9, 150.6, 153.2,
154.1, 169.2, 169.8, 170.3; Anal. Calcd. for C28H30N4O10S:
C, 54.72; H, 4.92; N, 9.12; Found: C, 54.64; H, 5.03; N,
9.29.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-p-methoxyphenyl-4H-1,2,4-triazole (5e)
Yield: 75%; Mp: 148-150 °C; [a] 2D0 +4 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 1.98-2.01 (m, 12H), 3.79-
3.83 (m, 1H), 3.87 (s, 3H), 4.09 (dd, J = 12.6 & 2.1 Hz, 1H),
4.23 (dd, J = 12.6 & 4.5 Hz, 1H), 5.05-5.13 (m, 2H), 5.26 (t,
J = 9.3 Hz, 1H), 5.60 (d, J = 9.9 Hz, 1H), 6.98 (d, J = 9.0
Hz, 2H), 7.12 (d, J = 9.0 Hz, 2H), 7.30 (d, J = 6.3 Hz, 2H),
8.53 (d, J = 6.3 Hz, 2H); 13C NMR (75 MHz, CDCl3) d
20.4, 20.5, 55.5, 61.3, 67.6, 69.6, 73.5, 75.9, 83.5, 115.2,
121.2, 125.3, 128.4, 133.7, 150.0, 151.0, 152.9, 160.8,
169.3, 169.4, 169.8, 170.4; Anal. Calcd. for C28H30N4O10S:
C, 54.72; H, 4.92; N, 9.12; Found: C, 54.43; H, 4.70; N,
9.07.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-o-ethoxyphenyl-4H-1,2,4-triazole (5b)
Yield: 89%; Mp: 77-78 °C; [a] 2D0 –12 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 1.09 (t, J = 6.9 Hz, 3H),
1.99-2.03 (m, 12H), 3.74-3.85 (m, 2H), 3.92-3.99 (m, 1H),
4.02-4.12 (m, 1H), 4.19-4.30 (m, 1H), 5.02-5.15 (m, 2H),
5.23-5.30 (m, 1H), 5.54-5.63 (m, 1H), 6.98-7.08 (m, 2H),
7.15-7.25 (m, 1H), 7.32 (d, J = 5.7 Hz, 2H), 7.53-7.65 (m,
1H), 8.54 (d, J = 5.7 Hz, 2H); 13C NMR (75 MHz, CDCl3) d
14.1, 20.4, 61.4, 64.1, 67.6, 69.8, 73.5, 76.0, 83.4, 84.2,
113.0, 113.4, 120.9, 121.8, 128.3, 128.9, 132.0, 134.4,
150.0, 150.6, 153.3, 153.5, 169.3, 169.8, 170.3; Anal.
Calcd. for C29H32N4O10S: C, 55.41; H, 5.13; N, 8.91;
Found: C, 55.22; H, 5.30; N, 8.99.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-o-methylphenyl-4H-1,2,4-triazole (5f)
Yield: 71%; Mp: 138-140 °C; [a] 2D0 +5 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 1.94-2.02 (m, 15H), 3.80-
3.85 (m, 1H), 4.03-4.14 (m, 1H), 4.20-4.29 (m, 1H), 5.05-
5.14 (m, 2H), 5.25-5.32 (m, 1H), 5.64-5.76 (m, 1H), 7.14-
7.30 (m, 3H), 7.36-7.40 (m, 2H), 7.51 (t, J = 7.8 Hz, 1H),
8.53 (d, J = 5.7 Hz, 2H); 13C NMR (75 MHz, CDCl3) d
17.2, 20.5, 61.5, 67.8, 69.7, 73.6, 76.1, 83.7, 120.4, 127.7,
128.2, 131.2, 132.1, 133.8, 135.3, 135.6, 150.4, 150.9,
152.4, 169.3, 169.9, 170.4; Anal. Calcd. for C28H30N4O9S:
C, 56.18; H, 5.05; N, 9.36; Found: C, 55.95; H, 5.31; N,
9.46.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-p-ethoxyphenyl-4H-1,2,4-triazole (5c)
Yield: 74%; Mp: 125-127 °C; [a] 2D0 +2 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 1.46 (t, J = 7.2 Hz, 3H),
1.99-2.02 (m, 12H), 3.81-3.84 (m, 1H), 4.05-4.12 (m, 3H),
4.25 (dd, J = 12.6 & 4.2 Hz, 1H), 5.07-5.15 (m, 2H), 5.27 (t,
J = 9.3 Hz, 1H), 5.62 (d, J = 10.5 Hz, 1H), 6.97 (d, J = 9.3
Hz, 2H), 7.11 (d, J = 9.3 Hz, 2H), 7.30-7.33 (m, 2H), 8.53-
8.56 (m, 2H); 13C NMR (75 MHz, CDCl3) d 14.5, 20.4,
61.4, 63.9, 67.7, 69.7, 73.6, 76.1, 83.6, 115.7, 121.3, 125.2,
128.4, 133.8, 150.1, 151.1, 153.0, 160.3, 169.4, 169.8,
170.4; Anal. Calcd. for C29H32N4O10S: C, 55.41; H, 5.13;
N, 8.91; Found: C, 55.19; H, 5.35; N, 8.92.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-m-methylphenyl-4H-1,2,4-triazole (5g)
Yield: 65.1%; Mp: 175-176 °C; [a] 2D0 +3 (c 1,
1
CH2Cl2); H NMR (300 MHz, CDCl3) d 1.94-1.97 (m,
12H), 2.35 (s, 3H), 3.75-3.80 (m, 1H), 4.02-4.06 (m, 1H),
4.21 (dd, J = 12.9 & 4.5 Hz, 1H), 5.02-5.10 (m, 2H), 5.23 (t,

838 J. Chin. Chem. Soc., Vol. 55, No. 4, 2008
Zhang et al.
J = 9.3 Hz, 1H), 5.57 (d, J = 10.8 Hz, 1H), 6.96-6.99 (m,
2H), 7.24 (d, J = 5.7 Hz, 2H), 7.33-7.35 (m, 2H), 8.48 (d, J
= 5.7 Hz, 2H); 13C NMR (75 MHz, CDCl3) d 20.4, 20.5,
21.1, 61.4, 67.7, 69.7, 73.6, 76.1, 83.8, 121.2, 124.2, 127.6,
129.9, 131.4, 133.1, 133.7, 140.6, 150.1, 150.6, 152.8,
169.2, 169.3, 169.7, 170.3; Anal. Calcd. for C28H30N4O9S:
C, 56.18; H, 5.05; N, 9.36; Found: C, 56.04; H, 5.34; N,
9.49.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-p-bromophenyl-4H-1,2,4-triazole (5k)
Yield: 53%; Mp: 190-192 °C; [a] 2D0 +1 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 1.95-1.99 (m, 12H), 3.74-
3.80 (m, 1H), 4.06 (dd, J = 12.3 & 1.8 Hz, 1H), 4.18 (dd, J =
12.3 & 4.5 Hz, 1H), 5.01-5.10 (m, 2H), 5.23 (t, J = 9.0 Hz,
1H), 5.51 (d, J = 10.5 Hz, 1H), 7.08 (d, J = 9.0 Hz, 2H),
7.25 (d, J = 5.1 Hz, 2H), 7.62 (d, J = 9.0 Hz, 2H), 8.53 (d, J
= 5.1 Hz, 2H); 13C NMR (75 MHz, CDCl3) d 20.4, 20.5,
61.3, 67.6, 69.7, 73.4, 76.1, 83.9, 121.4, 124.9, 128.8,
132.0, 133.4, 150.2, 152.8, 169.3, 169.4, 169.8, 170.3;
Anal. Calcd. for C27H27BrN4O9S: C, 48.88; H, 4.10; N,
8.44; Found: C, 49.10; H, 4.28; N, 8.64.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-p-methylphenyl-4H-1,2,4-triazole (5h)
Yield: 73.7%; Mp: 177-179 °C; [a] 2D0 +1 (c 1,
1
CH2Cl2); H NMR (300 MHz, CDCl3) d 1.99-2.02 (m,
12H), 2.46 (s, 3H), 3.81-3.84 (m, 1H), 4.10 (dd, J = 12.3 &
1.8 Hz, 1H), 4.25 (dd, J = 12.3 & 4.5 Hz, 1H), 5.07-5.14
(m, 2H), 5.27 (t, J = 9.3 Hz, 1H), 5.62 (d, J = 10.2 Hz, 1H),
7.09 (d, J = 8.1 Hz, 2H), 7.29-7.32 (m, 4H), 8.54 (d, J = 6.3
Hz, 2H); 13C NMR (75 MHz, CDCl3) d 20.5, 21.3, 61.5,
67.8, 69.8, 73.7, 76.2, 83.8, 121.4, 127.0, 130.5, 130.9,
133.8, 141.1, 150.2, 150.8, 153.0, 169.5, 169.9, 170.5;
Anal. Calcd. for C28H30N4O9S: C, 56.18; H, 5.05; N, 9.36;
Found: C, 55.99; H, 4.79; N, 9.48.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-o-chlorophenyl-4H-1,2,4-triazole (5l)
Yield: 60.3%; Mp: 92-94 °C; [a] 2D0 -6 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 1.95-2.00 (m, 12H), 3.75-
3.80 (m, 1H), 3.99-4.09 (m, 1H), 4.17-4.22 (m, 1H), 4.99-
5.12 (m, 2H), 5.24 (t, J = 9.0 Hz, 1H), 5.49-5.55 (m, 1H),
7.25-7.37 (m, 3H), 7.43-7.47 (m, 1H), 7.51-7.57 (m, 2H),
8.52 (d, J = 6.0 Hz, 2H); 13C NMR (75 MHz, CDCl3) d
20.4, 20.5, 30.8, 61.4, 67.6, 69.8, 73.5, 76.1, 84.0, 120.8,
128.5, 129.5, 129.9, 131.0, 131.2, 132.3, 133.7, 150.2,
150.6, 153.0, 169.4, 169.8, 169.9, 170.4; Anal. Calcd. for
C27H27ClN4O9S: C, 52.39; H, 4.40; N, 9.05; Found: C,
52.41; H, 4.15; N, 9.19.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-o-bromophenyl-4H-1,2,4-triazole (5i)
Yield: 64.4%; Mp: 84-86 °C; [a] 2D0 -5 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 1.99-2.04 (m, 12H), 3.78-
3.82 (m, 1H), 4.03-4.13 (m, 1H), 4.22-4.27 (m, 1H), 5.03-
5.17 (m, 2H), 5.27 (t, J = 9.3 Hz, 1H), 5.58 (d, J = 9.9 Hz,
1H), 7.29-7.39 (m, 3H), 7.46-7.52 (m, 2H), 7.75-7.78 (m,
1H), 8.56 (d, J = 6 Hz, 2H); 13C NMR (75 MHz, CDCl3) d
20.4, 61.4, 67.7, 69.9, 73.5, 76.1, 84.4, 120.8, 122.4, 129.1,
129.6, 130.0, 132.4, 132.7, 133.7, 134.1, 134.3, 150.2,
169.3, 169.4, 169.8, 170.3; Anal. Calcd. for C27H27BrN4O9S:
C, 48.88; H, 4.10; N, 8.44; Found: C, 49.10; H, 4.28; N,
8.64.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-m-chlorophenyl-4H-1,2,4-triazole (5m)
Yield: 57%; Mp: 161-162 °C; [a] 2D0 +1 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 1.98-2.03 (m, 12H), 3.75-
3.80 (m, 1H), 4.09 (dd, J = 12.3 & 1.8 Hz, 1H), 4.22 (dd, J =
12.3 & 4.5 Hz, 1H), 5.04-5.14 (m, 2H), 5.26 (t, J = 9.0 Hz,
1H), 5.52 (d, J = 9.9 Hz, 1H), 7.11 (d, J = 7.2 Hz, 1H),
7.26-7.29 (m, 3H), 7.43-7.48 (m, 1H), 7.54-7.57 (m, 1H),
8.57 (d, J = 6.0 Hz, 2H); 13C NMR (75 MHz, CDCl3) d
20.4, 30.8, 61.4, 67.7, 69.8, 73.5, 76.3, 84.2, 121.4, 125.7,
127.7, 131.0, 131.1, 133.4, 134.3, 135.9, 150.3, 169.3,
169.4, 169.8, 170.3; Anal. Calcd. for C27H27ClN4O9S: C,
52.39; H, 4.40; N, 9.05; Found: C, 52.64; H, 4.38; N, 9.32.
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-p-chlorophenyl-4H-1,2,4-triazole (5n)
Yield: 51%; Mp: 174-175 °C; [a] 2D0 +1 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 2.00-2.03 (m, 12H), 3.77-
3.83 (m, 1H), 4.08-4.12 (m, 1H), 4.23 (dd, J = 12.3 & 4.8
Hz, 1H), 5.07-5.15 (m, 2H), 5.28 (t, J = 9.0 Hz, 1H), 5.57
(d, J = 10.2 Hz, 1H), 7.18 (d, J = 8.7 Hz, 2H), 7.28-7.29 (m,
2H), 7.51 (d, J = 8.7 Hz, 2H), 8.58-8.59 (m, 2H); 13C NMR
3-S-(2¢,3¢,4¢,6¢-Tetra-O-acetyl-b-D-glucopyranosyl)-5-
(4-pyridyl)-4-m-bromophenyl-4H-1,2,4-triazole (5j)
Yield: 47.8%; Mp: 94-96 °C; [a] 2D0 +3 (c 1, CH2Cl2);
1H NMR (300 MHz, CDCl3) d 2.00-2.05 (m, 12H), 3.77-
3.82 (m, 1H), 4.08-4.13 (m, 1H), 4.24 (dd, J = 12.9 & 4.8
Hz, 1H), 5.07-5.16 (m, 2H), 5.28 (t, J = 9.3 Hz, 1H), 5.54
(d, J = 10.5 Hz, 1H), 7.16-7.18 (m, 1H), 7.30 (d, J = 4.5 Hz,
2H), 7.39-7.44 (m, 2H), 7.71-7.74 (m, 1H), 8.59 (d, J = 4.5
Hz, 2H); 13C NMR (75 MHz, CDCl3) d 20.8, 20.9, 61.7,
67.9, 70.0, 73.8, 76.5, 84.4, 121.7, 123.8, 126.5, 130.8,
131.7, 133.7, 134.2, 134.6, 150.6, 153.2, 169.6, 169.8,
170.2, 170.7; Anal. Calcd. for C27H27BrN4O9S: C, 48.88;
H, 4.10; N, 8.44; Found: C, 48.61; H, 4.09; N, 8.33.

Synthesis of Some New S-nucleosides
J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 839
(75 MHz, CDCl3) d 20.7, 20.9, 61.7, 68.0, 70.1, 73.8, 76.5,
84.3, 121.7, 129.0, 130.8, 131.9, 133.7, 137.1, 150.6,
153.2, 169.6, 169.7, 170.1, 170.6; Anal. Calcd. for
C27H27ClN4O9S: C, 52.39; H, 4.40; N, 9.05; Found: C,
52.49; H, 4.12; N, 9.31.
Found: C, 54.63; H, 5.47; N, 12.08.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-o-methoxyphenyl-4H-1,2,4-triazole (6d)
Yield: 90%; Mp: 127-129 °C; [a]2D0 -51 (c 1, CH3OH);
1H NMR (300 MHz, D2O) d 3.24-3.48 (m, 7H), 3.57-3.63
(m, 1H), 3.70-3.76 (m, 1H), 4.83-4.90 (m, 1H), 6.96-7.04
(m, 2H), 7.16-7.25 (m, 3H), 7.42-7.47 (m, 1H), 8.30 (d, J =
5.7 Hz, 2H); 13C NMR (75 MHz, D2O) d 55.8, 60.7, 69.0,
72.0, 77.1, 80.4, 86.2, 113.3, 121.0, 121.6, 121.8, 128.9,
132.9, 134.2, 149.4, 151.5, 153.9; Anal. Calcd. for
C20H22N4O6S: C, 53.80; H, 4.97; N, 12.55; Found: C,
53.56; H, 5.13; N, 12.66.
General Procedure for Preparation of Deacetylated
S-Nucleosides Derivatives of 1,2,4-Triazoles (6a-n)
The compound (5a-n) (0.2 g) was dissolved in dry
methanol and a stream of dry ammonia gas was passed
through the stirred solution for 1-2 hrs. The solution was
concentrated and the crude product was purified by column
chromatography.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-p-methoxyphenyl-4H-1,2,4-triazole (6e)
Yield: 91.5%; Mp: 138-140 °C; [a] 2D0 -49 (c 1,
CH3OH); 1H NMR (300 MHz, D2O) d 3.27-3.35 (m, 3H),
3.42-3.45 (m, 1H), 3.56-3.61 (m, 1H), 3.67 (s, 3H), 3.74 (d,
J = 11.7 Hz, 1H), 4.86 (d, J = 9.0 Hz, 1H), 6.88 (d, J = 8.7
Hz, 2H), 7.11 (d, J = 8.7 Hz, 2H), 7.17 (d, J = 5.7 Hz, 2H),
8.27 (d, J = 5.7 Hz, 2H); 13C NMR (75 MHz, D2O) d 55.7,
60.7, 69.1, 72.1, 77.1, 80.4, 86.0, 115.3, 122.5, 125.3,
129.0, 133.9, 149.3, 151.5, 153.6, 160.6; Anal. Calcd. for
C20H22N4O6S: C, 53.80; H, 4.97; N, 12.55; Found: C,
53.47; H, 5.15; N, 12.36.
pyridyl)-4-phenyl-4H-1,2,4-triazole (6a)
Yield: 95.2%; Mp: 134-136 °C; [a] 2D0 -49 (c 1,
CH3OH); 1H NMR (300 MHz, D2O) d 3.25-3.34 (m, 3H),
3.40-3.45 (m, 1H), 3.54-3.59 (m, 1H), 3.70-3.73 (m, 1H),
4.83 (d, J = 9.3 Hz, 1H), 7.13-7.20 (m, 4H), 7.37-7.49 (m,
3H), 8.26 (d, J = 6.3 Hz, 2H); 13C NMR (75 MHz, D2O) d
60.6, 69.0, 72.1, 77.1, 80.4, 86.1, 122.6, 127.7, 130.2,
131.0, 132.6, 133.8, 149.3, 151.0, 153.5; Anal. Calcd. for
C19H20N4O5S: C, 54.80; H, 4.84; N, 13.45; Found: C,
54.64; H, 4.72; N, 13.25.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-o-ethoxyphenyl-4H-1,2,4-triazole (6b)
Yield: 93.5%; Mp: 120-122 °C; [a] 2D0 -53 (c 1,
CH3OH); 1H NMR (300 MHz, D2O) d 0.81 (t, J = 7.2 Hz,
3H), 3.23-3.34 (m, 4H), 3.37-3.64 (m, 2H), 3.70-3.82 (m,
2H), 4.89 (d, J = 9.9 Hz, 1H), 6.96-7.04 (m, 2H), 7.21 (d, J
= 5.7 Hz, 2H), 7.27-7.30 (m, 1H), 7.42 (t, J = 7.8 Hz, 1H),
8.32 (d, J = 5.7 Hz, 2H); 13C NMR (75 MHz, D2O) d 13.7,
60.7, 64.7, 69.1, 72.0, 77.2, 80.4, 86.2, 114.0, 121.2, 121.9,
129.0, 132.8, 134.4, 149.4, 151.4, 153.0, 153.1, 154.0;
Anal. Calcd. for C21H24N4O6S: C, 54.77; H, 5.25; N, 12.17;
Found: C, 54.86; H, 5.07; N, 12.35.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-o-methylphenyl-4H-1,2,4-triazole (6f)
Yield: 89%; Mp: 124-126 °C; [a]2D0 -48 (c 1, CH3OH);
1H NMR (300 MHz, D2O) d 1.70 (s, 3H), 3.29-3.37 (m,
4H), 3.60-3.66 (m, 1H), 3.76 (t, J = 12.3 Hz, 1H), 4.95-4.99
(m, 1H), 7.20 (d, J = 6.0 Hz, 2H), 7.23-7.33 (m, 3H), 7.41
(t, J = 7.5 Hz, 1H), 8.30 (d, J = 6.0 Hz, 2H); 13C NMR (75
MHz, D2O) d 16.6, 60.7, 69.1, 72.1, 77.1, 80.4, 86.0, 121.8,
127.9, 128.3, 131.6, 132.0, 133.8, 135.7, 149.6, 151.6,
151.7, 153.3; Anal. Calcd. for C20H22N4O5S: C, 55.80; H,
5.15; N, 13.02; Found: C, 55.63; H, 5.43; N, 13.25.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-m-methylphenyl-4H-1,2,4-triazole (6g)
Yield: 98%; Mp: 158-160 °C; [a]2D0 -47 (c 1, CH3OH);
1H NMR (300 MHz, D2O) d 2.11 (s, 3H), 3.25-3.35 (m,
3H), 3.41-3.47 (m, 1H), 3.55-3.60 (m, 1H), 3.72 (d, J =
11.7 Hz, 1H), 4.87 (d, J = 9.9 Hz, 1H), 6.93 (m, 2H), 7.13
(d, J = 4.8 Hz, 2H), 7.23 (d, J = 4.8 Hz, 2H), 8.22-8.23 (m,
2H); 13C NMR (75 MHz, D2O) d 20.4, 60.7, 69.0, 72.1,
77.1, 80.4, 86.0, 122.5, 124.6, 127.9, 130.0, 131.6, 132.5,
133.9, 141.0, 149.3, 151.2, 153.3; Anal. Calcd. for
C20H22N4O5S: C, 55.80; H, 5.15; N, 13.02; Found: C,
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-p-ethoxyphenyl-4H-1,2,4-triazole (6c)
Yield: 92%; Mp: 123-125 °C; [a]2D0 -45 (c 1, CH3OH);
1H NMR (300 MHz, D2O) d 1.17 (t, J = 6.9 Hz, 3H), 3.30-
3.38 (m, 3H), 3.44-3.51 (m, 1H), 3.57-3.63 (m, 1H), 3.73-
3.77 (m, 1H), 3.84-3.91 (m, 2H), 4.92 (d, J = 9.9 Hz, 1H),
6.84 (d, J = 8.7 Hz, 2H), 7.10 (d, J = 8.7 Hz, 2H), 7.20 (d, J
= 5.4 Hz, 2H), 8.27 (d, J = 5.4 Hz, 2H); 13C NMR (75 MHz,
D2O) d 14.1, 60.8, 64.6, 69.1, 72.2, 77.2, 80.5, 86.0, 115.8,
122.6, 125.2, 129.1, 134.1, 149.3, 151.7, 153.4, 159.9;
Anal. Calcd. for C21H24N4O6S: C, 54.77; H, 5.25; N, 12.17;

840 J. Chin. Chem. Soc., Vol. 55, No. 4, 2008
Zhang et al.
55.94; H, 5.36; N, 12.98.
1H NMR (300 MHz, D2O) d 3.21-3.37 (m, 3H), 3.39-3.48
(m, 1H), 3.52-3.61 (m, 1H), 3.67-3.75 (m, 1H), 7.13-7.16
(m, 2H), 7.33-7.38 (m, 1H), 7.41-7.51 (m, 3H), 8.25-8.27
(m, 2H); 13C NMR (75 MHz, D2O) d 60.5, 68.9, 72.1, 77.1,
80.4, 86.6, 121.9, 129.1, 130.2, 130.8, 131.4, 133.0, 133.7,
149.5, 151.0, 153.7; Anal. Calcd. for C19H19ClN4O5S: C,
50.61; H, 4.25; N, 12.43; Found: C, 50.35; H, 4.53; N,
12.14.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-p-methylphenyl-4H-1,2,4-triazole (6h)
Yield: 91%; Mp: 136-138 °C; [a]2D0 -54 (c 1, CH3OH);
1H NMR (300 MHz, D2O) d 2.27 (s, 3H), 3.29-3.36 (m,
3H), 3.42-3.45 (m, 1H), 3.58-3.63 (m, 1H), 3.75 (d, J =
12.3 Hz, 1H), 4.85 (d, J = 9.9 Hz, 1H), 7.09 (d, J = 8.4 Hz,
2H), 7.20-7.25 (m, 4H), 8.31 (d, J = 5.1 Hz, 2H); 13C NMR
(75 MHz, D2O) d 20.5, 60.6, 69.0, 72.1, 77.1, 80.4, 86.0,
122.6, 127.4, 130.0, 130.7, 134.0, 141.8, 149.3, 151.2,
153.6; Anal. Calcd. for C20H22N4O5S: C, 55.80; H, 5.15; N,
13.02; Found: C, 56.04; H, 5.36; N, 13.28.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-m-chlorophenyl-4H-1,2,4-triazole (6m)
Yield: 91.2%; Mp: 132-134 °C; [a] 2D0 -47 (c 1,
CH3OH); 1H NMR (300 MHz, D2O) d 3.30-3.34 (m, 3H),
3.41-3.47 (m, 1H), 3.55-3.61 (m, 1H), 3.74 (d, J = 11.1 Hz,
1H), 4.83 (d, J = 10.2 Hz, 1H), 7.17-7.27 (m, 4H), 7.38-
7.40 (m, 2H), 8.29 (d, J = 6.0 Hz, 2H); 13C NMR (75 MHz,
D2O) d 60.7, 69.1, 72.1, 77.1, 80.4, 86.4, 122.7, 126.6,
127.8, 131.1, 131.5, 133.7, 135.0, 149.4, 150.8, 153.5;
Anal. Calcd. for C19H19ClN4O5S: C, 50.61; H, 4.25; N,
12.43; Found: C, 50.29; H, 4.16; N, 12.38.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-o-bromophenyl-4H-1,2,4-triazole (6i)
Yield: 92%; Mp: 138-140 °C; [a]2D0 -63 (c 1, CH3OH);
1H NMR (300 MHz, D2O) d 3.26-3.44 (m, 4H), 3.57-3.62
(m, 1H), 3.69-3.76 (m, 1H), 7.17-7.19 (m, 2H), 7.35-7.41
(m, 1H), 7.46-7.55 (m, 3H), 8.27-8.30 (m, 2H); 13C NMR
(75 MHz, D2O) d 60.9, 68.9, 72.2, 77.2, 80.4, 86.6, 121.8,
122.1, 129.7, 130.5, 131.8, 133.1, 133.7, 133.9, 149.6,
151.0, 153.6; Anal. Calcd. for C19H19BrN4O5S: C, 46.07;
H, 3.87; N, 11.31; Found: C, 45.89; H, 3.69; N, 11.45.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-m-bromophenyl-4H-1,2,4-triazole (6j)
Yield: 95.7%; Mp: 142-144 °C; [a] 2D0 -32 (c 1,
CH3OH); 1H NMR (300 MHz, D2O) d 3.29-3.39 (m, 3H),
3.41-3.47 (m, 1H), 3.57-3.63 (m, 1H), 3.76 (d, J = 12.3 Hz,
1H), 4.83-4.86 (m, 1H), 7.26 (d, J = 6.3 Hz, 2H), 7.29-7.39
(m, 2H), 7.50 (s, 1H), 7.64 (d, J = 7.8 Hz, 1H), 8.36 (d, J =
6.3 Hz, 2H); 13C NMR (75 MHz, D2O) d 60.7, 69.1, 72.1,
77.1, 80.4, 86.5, 122.8, 127.0, 130.7, 131.7, 133.8, 134.1,
149.4, 150.7, 153.7; Anal. Calcd. for C19H19BrN4O5S: C,
46.07; H, 3.87; N, 11.31; Found: C, 46.23; H, 3.65; N, 11.59.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-p-bromophenyl-4H-1,2,4-triazole (6k)
Yield: 98%; Mp: 152-154 °C; [a]2D0 -42 (c 1, CH3OH);
1H NMR (300 MHz, D2O) d 3.29-3.35 (m, 3H), 3.40-3.47
(m, 1H), 3.57-3.64 (m, 1H), 3.76 (d, J = 12.3 Hz, 1H), 7.24
(d, J = 8.1 Hz, 2H), 7.30 (d, J = 6.0 Hz, 2H), 7.64 (d, J = 8.1
Hz, 2H), 8.41 (d, J = 6.0 Hz, 2H); 13C NMR (75 MHz, D2O)
d 60.6, 69.1, 72.1, 77.1, 80.4, 86.4, 122.9, 124.7, 129.6,
131.8, 133.3, 133.9, 149.4, 150.7, 153.9; Anal. Calcd. for
C19H19BrN4O5S: C, 46.07; H, 3.87; N, 11.31; Found: C,
45.89; H, 4.06; N, 11.56.
3-S-(2¢,3¢,4¢,6¢-Tetrahydroxy-b-D-glucopyranosyl)-5-(4-
pyridyl)-4-p-chlorophenyl-4H-1,2,4-triazole (6n)
Yield: 92.2%; Mp: 140-142 °C; [a] 2D0 -43 (c 1,
CH3OH); 1H NMR (300 MHz, D2O) d 3.28-3.36 (m, 3H),
3.41-3.43 (m, 1H), 3.56-3.62 (m, 1H), 3.75 (d, J = 12.3 Hz,
1H), 7.27-7.31 (m, 4H), 7.46-7.49 (m, 2H), 8.39-8.41 (m,
2H); 13C NMR (75 MHz, D2O) d 60.6, 69.0, 72.1, 77.1,
80.4, 86.4, 122.9, 129.3, 130.3, 131.3, 133.9, 136.5, 149.4,
150.7, 153.9; Anal. Calcd. for C19H19ClN4O5S: C, 50.61;
H, 4.25; N, 12.43; Found: C, 50.47; H, 4.47; N, 12.69.
ACKNOWLEDGEMENTS
This work was supported by the National Natural Sci-
ence Foundation of China (NSFC, 20772051, 20572039),
the Key Project (02079), the Program (NCET-05-0880),
the Doctoral Funds from Chinese Ministry of Education of
P. R. China and Nature Science Foundation of Gansu prov-
ince (ZS051-A25-005).
Received November 9, 2007.
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