First novel synthesis of triazole thioglycosides as ribavirin analogues

Article abstract of DOI:10.1080/15257770.2017.1423079

This study reports a novel and efficient method for the synthesis of the first reported novel class of triazole thioglycosides. These series of compounds were designed through the reaction of potassium cyanocarbonimidodithioate 2 with hydrazine derivatives 3a-d in EtOH at room temperature to give the corresponding potassium 5-amino-1H-1,2,4-triazole-3-thiolates 4a-d. The latter compounds were treated with tetra-O-acetyl-α-D-glucopyranosyl bromide 6a and tetra-O-acetyl-α-D-galactopyranosyl bromide 6b in DMF at room temperature to give in high yields the corresponding triazole thioglycosides 7a-h. Treatment of triazole salts 4a–d with hydrochloric acid afforded the corresponding 3-mercaptotriazoles 5a-d. Compounds 5a-d were then reacted with bromoperacetylated sugars 6a,b in sodium hydride-DMF at ambient temperature to afford the thioglycosyl compounds 7a-h. Ammonolysis of the triazole thioglycosides 7a-h afforded the corresponding free thioglycosides 8a-h. The scope and limitation of the method is demonstrated. The structure of the reaction products was confirmed on the basis of their elemental analysis and spectral data (IR, ¹H NMR, MS and ¹³C NMR).

Full text of DOI:10.1080/15257770.2017.1423079

Nucleosides, Nucleotides and Nucleic Acids
ISSN: 1525-7770 (Print) 1532-2335 (Online) Journal homepage: http://www.tandfonline.com/loi/lncn20
First novel synthesis of triazole thioglycosides as
ribavirin analogues
Galal H. Elgemeie, Mamdouh A. Abu-Zaied & Galal A. Nawwar
To cite this article: Galal H. Elgemeie, Mamdouh A. Abu-Zaied & Galal A. Nawwar (2018): First
novel synthesis of triazole thioglycosides as ribavirin analogues, Nucleosides, Nucleotides and
Nucleic Acids, DOI: 10.1080/15257770.2017.1423079
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NUCLEOSIDES, NUCLEOTIDES AND NUCLEIC ACIDS
, VOL. , NO. , –
https://doi.org/./..
First novel synthesis of triazole thioglycosides as ribavirin
analogues
Galal H. Elgemeiea, Mamdouh A. Abu-Zaiedb, and Galal A. Nawwarb
aChemistry Department, Faculty of Science, Helwan University, Helwan, Cairo, Egypt; bGreen Chemistry
Department, National Research Centre, El Bohouth Street, Dokki, Giza, Egypt
ABSTRACT
ARTICLE HISTORY
Received  May 
Accepted  December 
This study reports a novel and efficient method for the synthesis
of the first reported novel class of triazole thioglycosides. These
series of compounds were designed through the reaction of
potassium cyanocarbonimidodithioate 2 with hydrazine deriva-
tives 3a-d in EtOH at room temperature to give the corresponding
potassium 5-amino-1H-1,2,4-triazole-3-thiolates 4a-d. The latter
compounds were treated with tetra-O-acetyl-α-D-glucopyranosyl
bromide 6a and tetra-O-acetyl-α-D-galactopyranosyl bromide 6b
in DMF at room temperature to give in high yields the cor-
responding triazole thioglycosides 7a-h. Treatment of triazole
salts 4a–d with hydrochloric acid afforded the corresponding
3-mercaptotriazoles 5a-d. Compounds 5a-d were then reacted
with bromoperacetylated sugars 6a,b in sodium hydride-DMF at
ambient temperature to afford the thioglycosyl compounds 7a-h.
Ammonolysis of the triazole thioglycosides 7a-h afforded the cor-
responding free thioglycosides 8a-h. The scope and limitation of
the method is demonstrated. The structure of the reaction prod-
ucts was confirmed on the basis of their elemental analysis and
spectral data (IR, 1H NMR, MS and 13C NMR).
KEYWORDS
Triazole thioglycosides;
ribavirin analogues; Hepatitis
C virus (HCV); potassium
cyanocarbonimidodithioate;
hetrocyclic thioglycosides
Introduction
Hepatitis C virus (HCV) incurs a major disease burden worldwide. Ribavirin is
a triazole nucleoside approved for HCV treatment and is a main member in suc-
cessful therapeutic protocols.[1] Ribavirin can cause a possible dangerous anemia
and can cause substantial teratogenic effects, including possible birth defects and
death (Figure 1).[2] Pregnant women should not use ribavirin during pregnancy.[3]
Many other negative but less serious effects have been noticed with ribavirin like
nausea, itching, dermatitis and fatigue. In view of the facts mentioned, design and
synthesis of ribavirin analogues as bioactive lead compounds will continue to be
explored.[4] As a part of our current project aimed towards examining synthetic
methods for preparation of S-glycosylated derivatives of heterocyclic nitrogen
bases, we have recently reported the synthesis and antiviral activity of many
CONTACT Galal H. Elgemeie
sity, Helwan, Cairo, Egypt.
elgemeie@yahoo.com
Chemistry Department, Faculty of Science, Helwan Univer-
©  Taylor & Francis Group, LLC

2
G. H. ELGEMEIE ET AL.
O
NH2
N
N
N
HO
O
H
H
H
H
OH
OH
Figure . Structure of ribavirin.
novel heterocyclic S-glycosides that have interesting cytotoxic activity, including
pyridine S-glcosides,[5,6] pyrimidine S-glycosides,[7,8] imidazole S-glycosides,[9]
oxadiazole S-glycosides,[10] thiophene S-glycosides,[11] quinoline S-glycosides,[12]
thienopyrazole S-glycosides[13] and purine S-glycosides.[14,15] We have mentioned
in previous research that the dihydropyridine thioglycoside compounds have a
strong activity against cancer cells.[16] In the light of these results and other previ-
ous researches,[17-19] the aim of this research is to design, synthesize and study the
biological activity of triazole thioglycosides carrying carbohydrate residues through
S-glycosidic bond formation. The prepared triazole thioglycosides are similar to the
known drug ribavirin, except that the glycosylation is on the exocyclic sulfur atom
and is not on ring nitrogen, and there is a substituted amino on ring triazole while
it is carboxamide in the drug ribavirin. To our knowledge, this is the first method
that is mentioned for the synthesis of triazole thioglycosides.
Results and discussion
The synthesis was initiated by the condensation of cyanamide 1 and carbon disulfide
in ethanolic potassium hydroxide in a simple one-step protocol to give the potas-
sium cyanocarbonimidodithioate 2 (Scheme 1). Compound 2 is readily reacted with
one equivalent of hydrazine derivatives 3a-d in ethanol at room temperature for
24 hours to give the corresponding potassium 5-amino-1H-1,2,4-triazole-3-thiolate
derivatives 4a–d in good yields. Acidification of the latter has resulted in the forma-
tion of the corresponding 3-mercaptotriazoles 5a-d. Compounds 4a–d undergoes
reaction with tetra-O-acetyl-α-D-glucopyranosyl bromide 6a and tetra-O-acetyl-α-
D-galactopyranosyl bromide 6b in DMF at ambient temperature to give in excellent
yields the corresponding triazole S-glycosides 7a-h. It has been confirmed that the
cis-(α) sugars reacted through an SN2 reaction mechanism to give the β-glycoside
reaction products.[20] The structures of 7a-h were proved according to their spectral
data (IR,13C NMR, 1H NMR). For example, the anomeric proton in the 1H NMR
spectrum for 7a appeared as a doublet at δ 5.62–5.63 ppm with a 10.7 Hz spin-
spin coupling constant indicating the β-configuration. The other glucose protons
appeared at δ 3.96–5.14 ppm. Compounds 7a–h can also be prepared by reaction of
the triazole-3-thiol derivatives 5a-d with halo sugars 6a,b in DMF-sodium hydride
at room temperature. The thioglycosides 7a-h reacted with MeOH-NH3 at ambient
temperature to give the deprotected thioglycoside derivatives 8a-h in good yields
(Schemes 2 and 3). The structures of 8a-h were proved based on spectral data. Thus,

NUCLEOSIDES, NUCLEOTIDES AND NUCLEIC ACIDS
3
H2N-CN
1
CS2 / EtOH
KOH / RT
R-NH-NH2
3a-d
R-NH-NH2
3a-d
N
SK
NC
AcOH /EtOH
RT/ 8h
EtOH
RT/ 24h
SK
2
R
R
NH2
N
NH2
N
N
N
N
H
N
RT
SH
SK
4a-d
5a-d
AcO
X
O
R
NH2
OAc
H
H
N
Y
Br
OAc
i) NaH/ DMF
ii) 6a,b
N
N
6a,b
AcO
X
S
3-10h -RT
DMF/ 8h - RT
O
H
OAc
H
Y
H
OAc
7a-h
Scheme . Synthetic pathway for triazole thioglycosides a-h.
7a-h
MeOH /NH3
RT /10 min
R
NH2
N
N
N
HO
X
S
O
H
OH
H
Y
H
OH
8a-h
Scheme . Synthetic pathway for triazole thioglycosides a-h.

4
G. H. ELGEMEIE ET AL.
3,4,5
R
a
H
C6H5
b
c
4-NO2-C6H4
2,4-di NO2-C6H3
d
X
7
a
R
7
e
f
R
Y
X
H
Y
OAc
H
H
OAc
OAc
H
H
C6H5
C6H5
b
OAc
OAc
OAc
H
4-NO2-C6H4
g
c
H
H
4-NO2-C6H4
OAc
OAc
H
H
d
2,4-di NO2-C6H3
h
2,4-di- NO2-C6H3
8
e
X
R
Y
X
8
a
R
Y
H
H
H
OH
OH
H
OH
OH
OH
OH
H
H
C6H5
C6H5
f
b
c
g
h
OH
OH
H
H
4-NO2-C6H4
4-NO2-C6H4
H
H
2,4-di NO2-C6H3
2,4-di NO2-C6H3
d
Scheme . List of synthesized derivatives ,,a-d; a-h; a-h.
the anomeric proton in the 1H NMR spectrum for 8a appeared as a doublet with
J1,2 = 9.6 Hz at δ 4.62–4.63, confirming the presence of only the β-D-configuration.
In conclusion, a novel synthesis of an interesting new class of triazole thiogly-
cosides is reported. The results represent a new, simple and economically effective
method for the synthesis of ribavirin drug analogues. The simple and ambient tem-
perature reaction conditions, clean reaction products, and availability of starting
materials make this approach innovative and useful to the present methods for the
formation of triazole glycosides. Further investigations on the use of this method
for the preparation of other biologically interesting glycosides will be investigated.
The prepared triazole thioglycosides are promising as good starting materials for
the preparation of other interesting carbohydrate compounds.
Experimental
All melting points were measured on a Gallenkamp melting point apparatus. The
1H NMR and 13C NMR spectra were measured on a Jeol-500 MHz spectrometer in
DMSO-d6 or CDCl3 using Si(CH3)4 as an internal standard at the National Research
Centre, Cairo, Egypt. Elemental analyses were carried out at the Microanalytical
unit, Faculty of Science, Cairo University. Progress of the reactions was monitored
by TLC using aluminum sheets coated with silica gel F254 (Merck). Viewing under a
short-wavelength UV lamp effected detection. Tetra-O-acetyl-α-D-glucopyranosyl
bromide 6a and tetra-O-acetyl-α-D-galactopyranosyl bromide 6b were prepared
according to literature procedures.[21] Compound 4a was previously reported.[22]

NUCLEOSIDES, NUCLEOTIDES AND NUCLEIC ACIDS
5
General procedure for the synthesis of (4a-d)
To potassium cyanocarbonimidodithioate 2 (10 mmol) in absolute ethanol (20 mL)
was added hydrazine derivatives 3a-d (10 mmol). The reaction mixture was stirred
at room temperature until completion (TLC, 24 h). A precipitate was formed was
filtered off and recrystallized from appropriate solvent to give compounds 4a-d.
Potassium -amino--phenyl-H-,,-triazole--thiolate (b)
Yellow solid; (EtOH); yield (84%); mp >300°C; IR (KBr, cm−1) υ 3410,3382 (NH2),
3039 (CH aromatic). C8H7KN4S (230.33).
Potassium -amino--(-nitrophenyl)-H-,,-triazole--thiolate (c)
Yellow solid; (EtOH); yield (82%); mp >300°C; IR (KBr, cm−1) υ 3368,3345 (NH2),
3036 (CH aromatic). C8H6KN5O2S (275.33).
Potassium -amino--(,-dinitrophenyl)-H-,,-triazole--thiolate (d)
White solid; (EtOH); yield (82%); mp >300°C; IR (KBr, cm−1) υ 3379,3346 (NH2),
3046 (CH aromatic). C8H5KN6O4S (320.33).
General procedure for the synthesis of (5a-d)
To a solution of compound 4a-d (10 mmol) in 20 ml water, drops of hydrochlo-
ric acid (36%) was dropped at room temperature (25oC) till just neutral. After an
additional stirring, a precipitate thus formed was filtered off and crystallized from
methanol to give 5a-d as yellow solid.
-Amino-H-,,-triazole--thiol (a)
Yellow solid; (EtOH); yield (95%); mp 254–255°C; IR (KBr, cm−1) υ 3388 (NH2),
1
=
3364 (NH), 1609 (C N); H NMR (500 MHz, DMSO): δ 6.83 (s, D2O exch., 2H,
NH2), 10.44 (s, D2O exch., 1H, NH), 12.89 (s, D2O exch., 1H, SH). Anal. Calcd. For.
C2H4N4S (116.14): C, 20.68; H, 3.47; N, 48.24; S, 27.61. Found: C, 20.54; H, 3.35; N,
48.16; S, 27.54%.
-Amino--phenyl-H-,,-triazole--thiol (b)
Yellow solid; (EtOH); yield (77%); mp 240–242°C; IR (KBr, cm−1) υ 3384, 3363
1
(NH2), 3034 (CH aromatic); H NMR (500 MHz, DMSO): δ 6.74 (s, D2O exch.,
2H, NH2), 7.35-7.76 (m, 5H, C6H5), 13.45 (s, D2O exch., 1H, SH); 13C NMR: δ
123.66 (2C, Ar-C), 135.54 (3C, Ar-C), 143.67 (Ar-C), 158.35 (C-3), 158.63 (C-5).
Anal. Calcd. For. C8H8N4S (192.24): C, 49.98; H, 4.19; N, 29.14; S, 16.68. Found: C,
49.86; H, 4.11; N, 29.10; S, 16.56%.
-Amino--(-nitrophenyl)-H-,,-triazole--thiol (c)
Yellow solid; (EtOH); yield (77%); mp 248–249°C; IR (KBr, cm−1) υ 3389, 3355
1
=
(NH2), 3076 (CH aromatic), 1604 (C N); H NMR (500 MHz, DMSO): 6.68 (s,

6
G. H. ELGEMEIE ET AL.
D2O exch., 2H, NH2), 8.51-8.64 (m, 4H, C6H4), 13.22 (s, D2O exch., 1H, SH). Anal.
Calcd. For. C8H7N5O2S (237.24): C, 40.50; H, 2.97; N, 29.52; S, 13.52. Found: C,
40.46; H, 2.88; N, 29.43; S, 13.46%.
-Amino--(,-dinitrophenyl)-H-,,-triazole--thiol (d)
Yellow solid; (EtOH); yield (84%); mp 226–228°C; IR (KBr, cm−1) υ 3369, 3346
1
=
(NH2), 3084 (CH aromatic), 1602 (C N); H NMR (500 MHz, DMSO): δ 6.68
(s, D2O exch., 2H, NH2), 8.26-8.97 (m, 3H, C6H3), 13.24 (s, 1H, SH); 13C NMR:
δ 123.11 (Ar-C), 126.82 (Ar-C), 129.44 (Ar-C), 137.25 (Ar-C), 151.36 (Ar-C),
152.41 (Ar-C), 156.95 (C-3), 169.13 (C-5). Anal. Calcd. For. C8H6N6O4S (282.24):
C, 34.04; H, 2.14; N, 29.78; S, 11.36. Found: C, 34.01; H, 2.10; N, 29.66; S,
11.24%.
General procedure for the synthesis of (7a-h)
Methode A
To a solution of 4a-d (10 mmol) in dry DMF (20 ml) a solution of 2,3,4,6-tetra-
O-acetyl-α-D-gluco or (galacto) pyronosyl bromide 6a,b (10 mmol) was dropped
within 30 min. Stirring was continued for 8h. After completion, the reaction mixture
was poured into ice water and the resulting precipitate was collected by filtration,
dried and recrystallized by using an appropriate solvent to give compounds 7a-h.
Methode B
To a solution of 5a-d (10 mmol) in dry DMF (20 ml), NaH (15 mmol) was added por-
tionwise through 15 min and the solution stirred at room temperature for another
30 min. Then a solution of 2,3,4,6-tetra-O-acetyl-α-D-gluco- or galactopyronosyl
bromide 6a,b in DMF (10 mmol) was dropped within 30 min and the reaction mix-
ture was stirred at room temperature until completion (TLC, 3–10 h). After com-
pletion, the reaction mixture was poured on ice water and the resulting precipitate
was collected by filtration, dried and recrystaiized by using an appropriate solvent
to give compounds 7a-h.
-(ꢀ,ꢀ,ꢀ,ꢀ-Tetra-O-acetyl-β-D-glucopyranosylthio)-H-,,-triazol--amine (a)
White solid; (EtOH); yield (method A: 76%, method B: 65%); mp 244–246°C; IR
−1
=
=
(KBr, cm ) υ 3381 (NH2), 3365 (NH), 2942 (CH), 1752 (C O), 1607 (C N);
1H NMR (500 MHz, DMSO): δ 1.99, 2.01, 2.02, 2.13 (4s, 12H, 4xOAc), 3.96-3.98
(m, 2H, 2H-6ꢀ), 4.46-4.49 (m, 1H, H-5ꢀ), 4.58 (t, 1H, J4 -3 = 9.1 Hz, J4 -5 = 6.9 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
H-4ꢀ), 4.66 (t, 1H, J3 -2 = 9.7 Hz, J3 -4 = 9.1 Hz, H-3ꢀ), 5.14 (t, 1H, J2 -1 = 10.7 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J2 -3 = 9.7 Hz, H-2ꢀ), 5.63 (d, 1H, J 1 -2 = 10.7 Hz, H-1ꢀ), 6.24 (s, D2O exch., 2H,
NH2), 10.53 (s, D2O exch., 1H, NH); 13C NMR: δ 22.44 (4xOAc), 62.54 (C-6ꢀ),
68.78 (C-5ꢀ), 69.46 (C-4ꢀ), 72.82 (C-3ꢀ), 75.33 (C-2ꢀ), 82.21 (C-1ꢀ), 160.24 (C-5),
ꢀ
ꢀ
ꢀ
ꢀ
=
163.11 (C-3), 174.45 (4C O). Anal. Calcd. For C16H22N4O9S (446.43): C, 43.05;
H, 4.97; N, 12.55; S, 7.18. Found: C, 43.01; H, 4.86; N, 12.48; S, 7.12%.

NUCLEOSIDES, NUCLEOTIDES AND NUCLEIC ACIDS
7
-(ꢀ,ꢀ,ꢀ,ꢀ-Tetra-O-acetyl-β-D-glucopyranosylthio)--phenyl)-H-,,-triazol--
amine (b)
White solid; (EtOH); yield (method A: 77%, method B: 63%); mp 235–237°C; IR
−1
=
(KBr, cm ) υ 3386, 3364 (NH2), 3053 (CH aromatic), 2965 (CH), 1749 (C O);
1H NMR (500 MHz, DMSO): δ 1.99, 2.05, 2.12, 2.14 (4s, 12H, 4xOAc), 3.97-4.12
(m, 2H, 2H-6ꢀ), 4.22-4.36 (m, 1H, H-5ꢀ), 4.35 (t, 1H, 1H, J4 -3 = 8.9 Hz, J4 -5
=
ꢀ
ꢀ
ꢀ
ꢀ
6.4 Hz, H-4ꢀ), 4.48 (t, 1H, J3 -2 = 9.4 Hz, J3 -4 = 8.9 Hz, H-3ꢀ), 4.64 (t, 1H, J2 -1
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
= 10.8 Hz, J2 -3 = 9.4 Hz, H-2ꢀ), 5.49 (d, 1H, J1 -2 = 10.8 Hz, H-1ꢀ), 6.67 (s, D2O
exch., 2H, NH2), 7.34–7.62 (m, 5H, C6 H5); 13C NMR: δ 22.46 (4xOAc), 62.54
(C-6ꢀ), 69.25 (C-5ꢀ), 70.32 (C-4ꢀ), 72.36 (C-3ꢀ), 74.53 (C-2ꢀ), 82.68 (C-1ꢀ), 125.24
(2C, Ar-C), 134.46 (3C, Ar-C), 141.31 (Ar-C), 159.11 (C-5), 165.28 (C-3), 174.41
ꢀ
ꢀ
ꢀ
ꢀ
=
(4C O). Anal. Calcd. For C22H26N4O9S (522.53): C, 50.57; H, 5.02; N, 10.72; S,
6.14. Found: C, 50.51; H, 5.00; N, 10.54; S, 6.10%.
-(ꢀ,ꢀ,ꢀ,ꢀ-Tetra-O-acetyl-β-D-glucopyranosylthio)--(-nitrophenyl)-H-,,-
triazol--amine (c)
White solid; (EtOH); yield (method A: 82%, method B: 75%); mp 216–218°C; IR
−1
=
(KBr, cm ) υ 3390, 3377 (NH2), 3033(CH aromatic), 2956 (CH), 1751 (C O),
1
=
1608 (C N); H NMR (500 MHz, DMSO): δ 1.99, 2.04, 2.08, 2.10 (4s, 12H, 4xOAc),
4.02-4.18 (m, 2H, 2H-6ꢀ), 4.31-4.42 (m, 1H, H-5ꢀ), 4.43 (t, 1H, 1H, J4 -3 = 8.9 Hz,
ꢀ
ꢀ
J4 -5 = 6.9 Hz, H-4ꢀ), 4.62 (t, 1H, J3 -2 = 9.4 Hz, J3 -4 = 8.9 Hz, H-3ꢀ), 4.72 (t, 1H,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J2 -1 = 10.7 Hz, J2 -3 = 9.4 Hz, H-2ꢀ), 5.45 (d,1H, J 1 -2 = 10.7 Hz, H-1ꢀ), 6.56 (s,
D2O exch., 2H, NH2), 8.27–8.65 (m, 4H, C6 H4); 13C NMR: δ 21.46 (4xOAc), 62.38
(C-6ꢀ), 69.54 (C-5ꢀ), 69.85 (C-4ꢀ), 73.61 (C-3ꢀ), 74.55 (C-2ꢀ), 83.34 (C-1ꢀ), 122.84
(2C, Ar-C), 132.53 (2C, Ar-C), 152.63 (Ar-C), 158.61 (Ar-C), 158.12 (C-5), 164.26
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
=
(C-3), 172.51 (4C O). Anal. Calcd. For C22H25N5O11S (567.53): C, 46.56; H, 4.44;
N, 12.34; S, 5.65. Found: C, 46.49; H, 4.36; N, 12.25; S, 5.60%.
-(,-Dinitrophenyl)--(ꢀ,ꢀ,ꢀ,ꢀ-tetra-O-acetyl-β-D-glucopyranosylthio)-H-,,-
triazol--amine (d)
1
White solid; (EtOH); yield (method A 80%, method B: 75%); mp 208–210°C; H
NMR (500 MHz, DMSO): δ 1.99, 2.02, 2.08, 2.11 (4s, 12H, 4xOAc), 4.02-4.13 (m,
2H, 2H-6ꢀ), 4.28-4.36 (m, 1H, H-5ꢀ), 4.56 (t, 1H, 1H, J4 -3 = 9.1 Hz, J4 -5 = 6.6 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
H-4ꢀ), 4.64 (t, 1H, J3 -2 = 9.3 Hz, J3 -4 = 9.1 Hz, H-3ꢀ), 4.82 (t, 1H, J2 -1 = 10.2 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J2 -3 = 9.3 Hz, H-2ꢀ), 5.62 (d, 1H, J 1 -2 = 10.2 Hz, H-1ꢀ), 6.48 (s, D2O exch., 2H,
NH2), 8.33–8.89 (m, 3H, C6 H3); 13C NMR: δ 21.44 (4xOAc), 62.11 (C-6ꢀ), 68.26
(C-5ꢀ), 69.76 (C-4ꢀ), 70.12 (C-3ꢀ), 71.86 (C-2ꢀ), 83.47 (C-1ꢀ), 122.25 (Ar-C), 130.47
(Ar-C), 132.74 (Ar-C), 139.62 (Ar-C), 151.48 (Ar-C), 152.61 (Ar-C), 158.63 (C-5),
ꢀ
ꢀ
ꢀ
ꢀ
=
165.26 (C-3), 174.16 (4C O). Anal. Calcd. For C22H24N6O13S (612.52): C, 43.14;
H, 3.95; N, 13.72; S, 5.23. Found: C, 43.10; H, 3.80; N, 13.64; S, 5.13%.
-(ꢀ,ꢀ,ꢀ,ꢀ-Tetra-O-acetyl-β-D-glucopyranosylthio)-H-,,-triazol--amine (e)
White solid; (EtOH); yield (method A: 79%, method B: 70%); mp 252–254°C; 1H
NMR (500 MHz, DMSO): δ 2.02, 2.04, 2.09, 2.11 (4s, 12H, 4xOAc), 3.99-4.03

8
G. H. ELGEMEIE ET AL.
(m, 2H, 2H-6ꢀ), 4.12-4.27 (m, 1H, H-5ꢀ), 4.34 (t, 1H, 1H, J4 -3 = 2.4 Hz,
ꢀ
ꢀ
J4 -5 = 3.1 Hz, H-4ꢀ), 4.48 (t, 1H, J3 -2 = 9.2 Hz, J3 -4 = 2.4 Hz, H-3ꢀ), 5.08 (t, 1H,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J2 -1 = 10.3 Hz, J2 -3 = 9.2 Hz, H-2 ), 5.43 (d, 1H, J 1 -2 = 10.3 Hz, H-1 ), 6.63 (s, D2O
exch., 2H, NH2), 10.43 (s, D2O exch., 1H, NH); 13C NMR: δ 21.64 (4xOAc), 62.66
(C-6ꢀ), 67.62 (C-5ꢀ), 69.11 (C-4ꢀ), 70.54 (C-3ꢀ), 72.42 (C-2ꢀ), 84.13 (C-1ꢀ), 161.18
=
(C-5), 164.34 (C-3), 173.62 (4C O). Anal. Calcd. For C16H22N4O9S (446.43): C,
43.05; H, 4.97; N, 12.55; S, 7.18. Found: C, 43.01; H, 4.86; N, 12.48; S, 7.12%.
-(ꢀ,ꢀ,ꢀ,ꢀ-Tetra-O-acetyl-β-D-galactopyranosylthio)--phenyl)-H-,,-triazol--
amine (f)
White solid; (EtOH); yield (method A: 75%, method B: 67%); mp 248–250°C; IR
−1
=
(KBr, cm ) υ 3392, 3365 (NH2), 3048 (CH aromatic), 2955 (CH), 1744 (C O);
1H NMR (500 MHz, DMSO): δ 1.99, 2.05, 2.08, 2.17 (4s, 12H, 4xOAc), 3.98-4.01
(m, 2H, 2H-6ꢀ), 4.09-4.25 (m, 1H, H-5ꢀ), 4.28 (t, 1H, J4 -3 = 2.6 Hz, J4 -5 = 3.2 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
H-4ꢀ), 4.42 (t, 1H, J3 -2 = 9.0 Hz, J3 -4 = 2.6 Hz, H-3ꢀ), 4.55 (t, 1H, J2 -1 = 10.4 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J2 -3 = 9.0 Hz, H-2ꢀ), 5.37 (d, 1H, J 1 -2 = 10.4 Hz, H-1ꢀ), 6.59 (s, D2O exch., 2H,
NH2), 7.32–7.74 (m, 5H, C6 H5); 13C NMR: δ 22.26 (4xOAc), 62.64 (C-6ꢀ), 69.18
(C-5ꢀ), 71.81 (C-4ꢀ), 73.42 (C-3ꢀ), 74.69 (C-2ꢀ), 83.86 (C-1ꢀ), 123.33 (2C, Ar-C),
ꢀ
ꢀ
ꢀ
ꢀ
=
134.64 (3C, Ar-C), 143.41(Ar-C), 158.26 (C-5), 164.56 (C3), 172.68 (4C O). Anal.
Calcd. For C22H26N4O9S (522.53): C, 50.57; H, 5.02; N, 10.72; S, 6.14. Found: C,
50.51; H, 5.00; N, 10.54; S, 6.10%.
-(ꢀ,ꢀ,ꢀ,ꢀ-Tetra-O-acetyl-β-D-galactopyranosylthio)--(-nitrophenyl)-H-,,-
triazol--amine (g)
White so−li1d; (EtOH); yield (method A: 80%, method B: 75%); mp 238–240°C; IR
=
=
(KBr, cm ) υ 3387, 3365 (NH2), 2936 (CH aromatic), 1756 (C O), 1596 (C N);
1H NMR (500 MHz, DMSO): δ 1.98, 1.99, 2.06, 2.12 (4s, 12H, 4xOAc), 4.24-4.31
(m, 2H, 2H-6ꢀ), 4.36-4.52 (m, 1H, H-5ꢀ), 4.54 (t, 1H, J4 -3 = 2.8 Hz, J4 -5 = 2.6 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
H-4ꢀ), 4.58 (t, 1H, J3 -2 = 9.3 Hz, J3 -4 = 2.8 Hz, H-3ꢀ), 4.63 (t, 1H, J2 -1 = 10.6 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J2 -3 = 9.3 Hz, H-2ꢀ), 5.39 (d, 1H, J1 -2 = 10.6 Hz, H-1ꢀ), 6.46 (s, D2O exch., 2H,
NH2), 8.35–8.78 (m, 4H, C6H4); 13C NMR: δ 22.24 (4xOAc), 62.56 (C-6ꢀ), 68.84
(C-5ꢀ), 70.35 (C-4ꢀ), 72.84 (C-3ꢀ), 74.61 (C-2ꢀ), 84.52 (C-1ꢀ), 123.64 (2C, Ar-C),
130.36 (2C, Ar-C), 148.52 (Ar-C), 155.74 (Ar-C), 159.26 (C-5), 165.42 (C-3),
ꢀ
ꢀ
ꢀ
ꢀ
=
172.66(4C O). Anal. Calcd. For C22H25N5O11S (567.53): C, 46.56; H, 4.44; N,
12.34; S, 5.65. Found: C, 46.49; H, 4.36; N, 12.25; S, 5.60%.
-(,-Dinitrophenyl)--(ꢀ,ꢀ,ꢀ,ꢀ-tetra-O-acetyl-β-D-galactopyranosylthio)-H-,,
-triazol--amine (h)
White solid; (EtOH); yield (method A: 84%, method B: 75%); mp 242–244°C; 1H
NMR (500 MHz, DMSO): δ 1.98, 1.99, 2.00, 2.02 (4s, 12H, 4xOAc), 4.24-4.31 (m,
2H, 2H-6ꢀ), 4.36-4.47 (m, 1H, H-5ꢀ), 4.57 (t, 1H, J4 -3 = 2.6 Hz, J4 -5 = 2.4 Hz, H-
ꢀ
ꢀ
ꢀ
ꢀ
4ꢀ), 4.59 (t, 1H, J3 -2 = 9.1 Hz, J3 -4 = 2.6 Hz, H-3ꢀ), 4.73 (t, 1H, J2 -1 = 10.6 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J2 -3 = 9.1 Hz, H-2ꢀ), 5.55 (d, 1H, J1 -2 = 10.6 Hz, H-1ꢀ), 6.55 (s, D2O exch., 2H,
ꢀ
ꢀ
ꢀ
ꢀ

NUCLEOSIDES, NUCLEOTIDES AND NUCLEIC ACIDS
9
NH2), 8.36–8.87 (m, 3H, C6 H3); 13C NMR: δ 22.65 (4xOAc), 62.53 (C-6ꢀ), 69.46 (C-
5ꢀ), 70.43 (C-4ꢀ), 72.54 (C-3ꢀ), 74.46 (C-2ꢀ), 84.56 (C-1ꢀ), 123.44 (Ar-C), 134.26 (2Ar-
C), 135.96 (Ar-C), 152.66 (Ar-C), 156.61 (Ar-C), 157.82 (C-5), 164.63 (C-3), 174.54
=
(4C O). Anal. Calcd. For C22H24N6O13S (612.52): C, 43.14; H, 3.95; N, 13.72; S,
5.23. Found: C, 43.10; H, 3.80; N, 13.64; S, 5.13%.
General procedure for the synthesis of (8a-h)
Dry gaseous of ammonia was passed through a solution of protected nucleoside
7a-h (10 mmol) in dry methanol (20 mL) for 10 min with cooling and stirring,
then the reaction mixture was stirred at room temperature until the reaction was
judged complete by TLC (9-10h) using (CHCl3/MeOH 9:1) (Rf, 0.54-0.56). The
resulting mixture was concentrated under reduced pressure to afford a solid residue
which washed several times by boiling chloroform. The residue was dried, purified
by column chromatography using chloroform/methanol (9:1) and crystallized from
appropriate solvent to give corresponding compounds 8a-h.
-(β-D-Glucopyranosylthio)-H-,,-triazol--amine (a)
White solid; (EtOH); yield (69%); mp 172–173°C; IR (KBr, cm−1) υ 3558 (OH),
1
=
3376,3339 (NH2), 3251 (NH), 2949 (CH), 1614 (C N); H NMR (500 MHz,
CDCl3) δ 3.32-3.41 (m, 2H, 2H-6ꢀ), 3.64-3.72 (m, 1H, H-5ꢀ), 4.02 (t, 1H, J4 -3
=
ꢀ
ꢀ
8.9 Hz, J4 -5 = 6.6 Hz, H-4ꢀ), 4.22 (t, 1H, J3 -2 = 9.6 Hz, J3 -4 = 8.9 Hz, H-3ꢀ), 4.36
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
(t, 1H, J2 -1 = 9.6 Hz, J2 -3 = 9.6 Hz, H-2 ), 4.63 (d, 1H, J1 -2 = 9.6 Hz, H-1ꢀ), 4.86 (s,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
–
–
–
–
D2O exch., 1H, 6 OH), 4.98 (s, D2O exch., 3H, 2 OH, 3 OH, and 4 OH), 6.42
(s, D2O exch., 2H, NH2), 10.78 (s, D2O exch., 1H, NH); 13C NMR: δ 62.16 (C-6ꢀ),
68.24 (C-5ꢀ), 69.56 (C-4ꢀ), 72.48 (C-3ꢀ), 74.52 (C-2ꢀ), 86.32 (C-1ꢀ), 161.28 (C-5),
163.12 (C-3). Anal. Calcd. For C8H14N4O5S (278.29): C, 34.53; H, 5.07; N, 20.13; S,
11.52. Found: C, 34.40; H, 5.01; N, 20.09; S, 11.43%.
-(β-D-Glucopyranosylthio)--phenyl-H-,,-triazol--amine (b)
White solid; (EtOH); yield (78%); mp 182–183°C; IR (KBr, cm−1) υ 3514 (OH),
1
=
3397, 3356 (NH2), 3056 (CH aromatic), 1615 (C N); H NMR (500 MHz, CDCl3)
δ 3.54-3.65 (m, 2H, 2H-6ꢀ), 3.74-3.81 (m,1H, H-5ꢀ), 4.18 (t, 1H, J4 -3 = 8.6 Hz,
ꢀ
ꢀ
J4 -5 = 6.4 Hz, H-4ꢀ), 4.38 (t, 1H, J3 -2 = 10.1 Hz, J3 -4 = 8.6 Hz, H-3ꢀ), 4.42 (t, 1H,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J2 -1 = 10.9 Hz, J2 -3 = 10.1 Hz, H-2ꢀ), 4.80 (d, 1H, J1 -2 10.9 Hz, H-1ꢀ), 4.84 (s,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
=
ꢀ
ꢀ
ꢀ
ꢀ
–
–
–
–
D2O exch., 1H, 6 OH), 5.00 (s, D2O exch., 3H, 2 OH, 3 OH, and 4 OH), 6.69
(s, D2O exch., 2H, NH2), 7.36–7.76 (m, 5H, C6H5); 13C NMR: δ 62.57 (C-6ꢀ), 71.68
(C-5ꢀ), 73.41 (C-4ꢀ), 75.23 (C-3ꢀ), 76.42 (C-2ꢀ), 85.84 (C-1ꢀ), 126.15 (2C, Ar-C),
130.41 (3C, Ar-C), 142.64 (Ar-C), 158.65 (C-5), 164.32 (C-3). Anal. Calcd. For
C14H18N4O5S (354.38): C, 47.45; H, 5.12; N, 15.81; S, 9.05. Found: C, 47.34; H,
5.06; N, 15.58; S, 9.01%.
-(β-D-Glucopyranosylthio)--(-nitrophenyl)-H-,,-triazol--amine (c)
White solid; (EtOH); yield (68%); mp 180–181°C; IR (KBr, cm−1) υ 3502 (OH),
1
=
3365, 3324 (NH2), 3049 (CH aromatic), 2955 (CH), 1615 (C N); H NMR

10
G. H. ELGEMEIE ET AL.
(500 MHz, CDCl3) δ 3.65-3.72 (m, 2H, 2H-6ꢀ), 3.86-3.89 (m, 1H, H-5ꢀ), 3.92 (t,
1H, J4 -3 = 8.3 Hz, J4 -5 = 6.9 Hz, H-4ꢀ), 4.24 (t, 1H, J3 -2 = 9.9 Hz, J3 -4 = 8.3 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
H-3ꢀ), 4.37 (t, 1H, J2 -1 = 10.4 Hz, J2 -3 = 9.9 Hz, H-2ꢀ), 4.46 (d, 1H, J1 -2 = 10.4 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
–
–
–
H-1 ), 4.82 (s, D2O exch., 1H, 6 OH), 5.04 (s, D2O exch., 3H, 2 OH, 3 OH, and
ꢀ
–
4 OH), 6.77 (s, D2O exch., 2H, NH2), 8.24–8.62 (m, 4H, C6H4). Anal. Calcd. For
C14H17N5O7S (399.38): C, 42.10; H, 4.29; N, 17.54; S, 8.03. Fond: C, 42.25; H, 4.12;
N, 17.36; S, 8.01%.
-(,-Dinitrophenyl)--(β-D-glucopyranosylthio)-H-,,-triazol--amine (d)
White solid; (EtOH); yield (72%); mp 186–187°C; 1H NMR (500 MHz, CDCl3) 3.47-
3.52 (m, 2H, 2H-6ꢀ), 3.63-3.69 (m, 1H, H-5ꢀ), 3.71 (t, 1H, J4 -3 = 9.2 Hz, J4 -5
=
ꢀ
ꢀ
ꢀ
ꢀ
8.4 Hz, H-4ꢀ), 3.84 (t, 1H, J3 -2 = 9.3 Hz, J3 -4 = 9.2 Hz, H-3ꢀ), 4.47 (t, 1H, J2 -1
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
= 10.7 Hz, J2 -3 = 9.3 Hz, H-2ꢀ), 4.52 (d, 1H, J1 -2 10.7 Hz, H-1ꢀ), 4.81 (s, D2O
ꢀ
ꢀ
ꢀ
ꢀ
=
ꢀ
ꢀ
ꢀ
ꢀ
–
–
–
–
exch., 1H, 6 OH), 4.95 (s, D2O exch., 3H, 2 OH, 3 OH, and 4 OH), 6.85 (s,
D2O exch., 2H, NH2), 8.35–9.23 (m, 3H, C6H3); 13C NMR: δ 62.21 (C-6ꢀ), 69.78
(C-5ꢀ), 72.43 (C-4ꢀ), 75.62 (C-3ꢀ), 78.66 (C-2ꢀ), 84.78 (C-1ꢀ), 123.41 (Ar-C), 128.76
(Ar-C), 133.84 (Ar-C), 136.53 (Ar-C), 154.52 (Ar-C), 156.31 (Ar-C), 158.35 (C-5),
165.46 (C-3). Anal. Calcd. For C14H16N6O9S (444.38): C, 37.84; H, 3.63; N, 18.91;
S, 7.22. Found: C, 37.52; H, 3.29; N, 18.82; S, 7.13%.
-(β-D-Galactopyranosylthio)-H-,,-triazol--amine (e)
White solid; (EtOH); yield (69%); mp 228–230°C; IR (KBr, cm−1) υ 3498 (OH),
1
=
3382,3346 (NH2), 3275 (NH), 2964 (CH), 1606 (C N); H NMR (500 MHz,
CDCl3) δ 3.22-3.28 (m, 2H, 2H-6ꢀ), 3.46-3.51 (m, 1H, H-5ꢀ), 3.64 (t, 1H, J4 -3
=
ꢀ
ꢀ
3.1 Hz, J4 -5 = 2.3 Hz, H-4ꢀ), 4.02 (t, 1H, J3 -2 = 9.1 Hz, J3 -4 = 3.1 Hz, H-3ꢀ), 4.23
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
(t, 1H, J2 -1 = 9.6 Hz, J2 -3 = 9.1 Hz, H-2ꢀ), 4.55 (d, 1H, J1 -2 9.6 Hz, H-1ꢀ), 4.89
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
=
ꢀ
ꢀ
ꢀ
ꢀ
–
–
–
–
(s, D2O exch., 1H, 6 OH), 4.99 (s, D2O exch., 3H, 2 OH, 3 OH, and 4 OH),
6.98(s, D2O exch., 2H, NH2), 10.89 (s, D2O exch., 1H, NH); 13C NMR: δ 62.42
(C-6ꢀ), 67.33 (C-5ꢀ), 69.21 (C-4ꢀ), 70.26 (C-3ꢀ), 76.43(C-2ꢀ), 84.57 (C-1ꢀ), 162.41
(C-5), 163.52 (C-3). Anal. Calcd. For C8H14N4O5S (278.29): C, 34.53; H, 5.07; N,
20.13; S, 11.52. Found: C, 34.40; H, 5.01; N, 20.09; S, 11.43%.
-(β-D-Galactopyranosylthio)--phenyl-H-,,-triazol--amine (f)
White solid; (EtOH); yield (72%); mp 210–212°C; IR (KBr, cm−1) υ 3520 (OH),
1
=
3383, 3347 (NH2), 3069 (CH aromatic), 2962 (CH), 1604 (C N); H NMR
(500 MHz, CDCl3) δ 3.22-3.27 (m, 2H, 2H-6ꢀ), 3.45-3.51 (m, 1H, H-5ꢀ), 3.62 (t,
1H, J4 -3 = 3.4 Hz, J4 -5 = 3.1 Hz, H-4ꢀ), 3.95 (t, 1H, J3 -2 = 9.3 Hz, J3 -4 = 3.4 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
H-3ꢀ), 4.26 (t, 1H, J2 -1 = 9.7 Hz, J2 -3 = 9.3 Hz, H-2ꢀ), 4.64 (d, 1H, J1 -2 9.7 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
=
ꢀ
ꢀ
ꢀ
ꢀ
–
–
–
H-1 ), 4.81 (s, D2O exch., 1H, 6 OH), 5.26 (s, D2O exch., 3H, 2 OH, 3 OH, and
ꢀ
13
–
4 OH), 6.88 (s, D2O exch., 2H, NH2), 7.32–7.75 (m, 5H, C6H5); C NMR: δ 62.36
(C-6ꢀ), 70.54 (C-5ꢀ), 72.66 (C-4ꢀ), 74.72 (C-3ꢀ), 76.41 (C-2ꢀ), 84.76 (C-1ꢀ), 126.11 (2C,
Ar-C), 132.29 (3C, Ar-C), 144.62 (Ar-C), 159.43 (C-5), 163.28 (C-3). Anal. Calcd.
For C14H18N4O5S (354.38): C, 47.45; H, 5.12; N, 15.81; S, 9.05. Found: C, 47.34; H,
5.06; N, 15.58; S, 9.01%.

NUCLEOSIDES, NUCLEOTIDES AND NUCLEIC ACIDS
11
-(β-D-Galactopyranosylthio)--(-nitrophenyl)-H-,,-triazol--amine (g)
White solid; (EtOH); yield (70%); mp 206–208°C; IR (KBr, cm−1) υ 3514 (OH),
1
=
3372, 3329 (NH2), 3052 (CH aromatic), 2968 (CH), 1610 (C N); H NMR
(500 MHz, CDCl3) δ 3.44-3.49 (m, 2H, 2H-6ꢀ), 3.62-3.69 (m, 1H, H-5ꢀ), 3.81 (t,
1H, J4 -3 = 2.7 Hz, J4 -5 = 2.5 Hz, H-4ꢀ), 4.19 (t, 1H, J3 -2 = 9.2 Hz, J3 -4 = 2.7 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
H-3ꢀ), 4.32 (t, 1H, J2 -1 = 10.6 Hz, J2 -3 = 9.2 Hz, H-2ꢀ), 4.48 (d, 1H, J1 -2 = 10.6 Hz,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
–
–
–
H-1 ), 4.87 (s, D2O exch., 1H, 6 OH), 5.15 (s, D2O exch., 3H, 2 OH, 3 OH, and
ꢀ
–
4 OH), 6.89 (s, D2O exch., 2H, NH2), 8.26–8.54 (m, 4H, C6H4). Anal. Calcd. For
C14H17N5O7S (399.38): C, 42.10; H, 4.29; N, 17.54; S, 8.03. Found: C, 42.25; H, 4.12;
N, 17.36; S, 8.01%.
-(,-Dinitrophenyl)--(β-D-galactopyranosylthio)-H-,,-triazol--amine (h)
White solid; (EtOH); yield (76%); mp 194–195°C; 1H NMR (500 MHz, CDCl3) 3.42-
3.45 (m, 2H, 2H-6ꢀ), 3.59-3.62 (m, 1H, H-5ꢀ), 3.64 (t, 1H, J4 -3 = 2.9 Hz, J4 -5
=
ꢀ
ꢀ
ꢀ
ꢀ
2.4 Hz, H-4ꢀ), 3.69 (t, 1H, J3 -2 = 10.1 Hz, J3 -4 = 2.9 Hz, H-3ꢀ), 4.26 (t, 1H, J2 -1
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
= 10.2 Hz, J2 -3 = 10.1 Hz, H-2ꢀ), 4.43 (d, 1H, J1 -2 10.2 Hz, H-1ꢀ), 4.86 (s, D2O
ꢀ
ꢀ
ꢀ
ꢀ
=
–
ꢀ
ꢀ
ꢀ
ꢀ
–
–
–
exch., 1H, 6 OH), 4.94 (s, D2O exch., 3H, 2 OH, 3 OH, and 4 OH), 6.75 (s, D2O
exch., 2H, NH2), 8.38–9.34 (m, 3H, C6H3); 13C NMR: δ 62.44 (C-6ꢀ), 67.94 (C-5ꢀ),
72.67 (C-4ꢀ), 74.73 (C-3ꢀ), 79.52 (C-2ꢀ), 85.94 (C-1ꢀ), 123.74 (Ar-C), 132.26 (Ar-C),
135.73 (Ar-C), 139.51 (Ar-C), 148.66 (Ar-C), 153.61 (Ar-C), 157.74 (C-5), 167.28
(C-3). Anal. Calcd. For C14H16N6O9S (444.38): C, 37.84; H, 3.63; N, 18.91; S, 7.22.
Found: C, 37.52; H, 3.29; N, 18.82; S, 7.13%.
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