Efficient TMG catalyzed synthesis of 1,2,3-triazoles

Article abstract of DOI:10.1016/j.crci.2013.05.006

A practical and efficient method for the synthesis of 1,2,3-triazoles via the cycloaddition reaction of azides and CH-acids in the presence of 1,1,3,3-tetramethylguanidine (TMG) in ethanol at 30 C has been reported. The simple experimental procedure, shor

Full text of DOI:10.1016/j.crci.2013.05.006

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C. R. Chimie xxx (2013) xxx–xxx
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Full paper/Memoire
Efficient TMG catalyzed synthesis of 1,2,3-triazoles
*
*
Fereshteh Ahmadi, Zeinab Noroozi Tisseh, Minoo Dabiri , Ayoob Bazgir
Department of Chemistry, Shahid Beheshti University, General Campus, Tehran 1983963113, Iran
A R T I C L E I N F O
A B S T R A C T
Article history:
A practical and efficient method for the synthesis of 1,2,3-triazoles via the cycloaddition
reaction of azides and CH-acids in the presence of 1,1,3,3-tetramethylguanidine (TMG) in
ethanol at 30 8C has been reported. The simple experimental procedure, short reaction
times, and good yields are the advantages of the present method.
Received 3 March 2013
Accepted after revision 13 May 2013
Available online xxx
´
ß 2013 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Keywords:
Azide
Triazole
Tetramethylguanidine
CH-acid
1. Introduction
under mild conditions for the highly regioselective
prepration of 1,4-disubstituted 1,2,3-triazoles in good
1,2,3-Triazoles are very interesting compounds and
have received considerable attention as a result of their
therapeutic value as cytostatic [1], antiproliferative agents
[2], and GABA-antagonists [3]. They are key intermediates
in the synthesis of antibiotic [4], antihistaminic agents [5],
muscarinic agonists for the treatment of Alzheimer’s
disease [6], and polyheterocycles with neuroleptic activity
[7]. Additionally, triazole derivatives have been widely
employed in industry [8–11]. Therefore, numerous meth-
ods have been reported for the preparation of 1,2,3-
triazoles, including the cyclization of triazenes [12,13], the
synthesis of triazoles by Wolff [14], and the cyclization of
yields. Notably, the reactions are only suited for terminal
alkynes, and this limitation largely restricts the diverse
application of this strategy in the preparation of 1,2,3-
triazoles. The azide/alkyne [3+2] strategy has shown a
broad variety of application prospects in polymeric
materials science [20–22]. Very recently, catalytic reaction
of azides and active or unactive methylene compounds has
proven to be a powerful strategy for the synthesis of a
variety of monocyclic and bicyclic 1,2,3-triazole deriva-
tives with different substituents. This triazole formation
approach is less developed and only a limited number of
catalysts have been reported [23–27]. Thus, the develop-
ment of a convenient and safe process using new catalysts
with high catalytic activity for the preparation of 1,2,3-
triazoles is an interesting target for investigation.
a
-diazoamides [15]. However, most of these protocols
have some disadvantages and require multistep synthetic
methods. Thermal Huisgen 1,3-dipolar cycloadditions of
azides and alkynes, because of the high activation energy
[16,17], are usually very slow and are likely to generate
mixtures of regioisomers. Recently, Sharpless [18] and
Meldal [19] reported copper(I)-catalyzed Huisgen 1,3-
dipolar cycloadditions of azides and alkynes (CuAAC)
Herein, we would like to report a facile, and practical
process for synthesis of 1,2,3-triazoles catalyzed by TMG
via a cycloaddition reaction of CH-acids and azides.
2. Results and discussion
Our initial experiments were focused on the reaction of
ethyl acetoacatate 1a (1 mmol) and 1-azido-4-nitroben-
zene 2a (1 mmol) as a model reaction in the presence of
*
Corresponding authors.
E-mail address: a_bazgir@sbu.ac.ir (A. Bazgir).
1631-0748/$ – see front matter ß 2013 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.crci.2013.05.006
Please cite this article in press as: Ahmadi F, et al. Efficient TMG catalyzed synthesis of 1,2,3-triazoles. C. R. Chimie
(2013), http://dx.doi.org/10.1016/j.crci.2013.05.006

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Scheme 1. Synthesis of ethyl 5-methyl-1-(4-nitrophenyl)-riazole-4-carboxylate.
Table 2
TMG in EtOH at 30 8C (Scheme 1). To study the effect of the
amount of catalyst, the reactions were carried out with
different amounts of TMG ranging from 10 to 20 mol%. It
was found that when increasing the amount of the TMG
from 10 to 15, and 20 mol %, the yields increased from 73 to
81 and 82%, respectively. It was found that 15 mol % TMG in
EtOH is sufficient to push this reaction forward. More
amounts of TMG did not improve the yields. When this
reaction was carried out without TMG, the yield of the
expected product was trace. To search for the optimal
reaction solvent, various solvents, such as EtOH, MeOH,
H2O, CHCl3, and MeCN were screened in the model reaction
at 30 8C. It was found that the reaction using EtOH resulted
in higher yield after 50 min (Scheme 1).
Comparison of efficiency of various catalysts in synthesis of triazolesa.
Catalyst
TMG
81
Proline
Et3N
41
Et2NH
35
Yield (%)
< 20
a
Ethyl acetoacatate 1a (1 mmol), 1-azido-4-nitrobenzene 2a (1 mmol)
and catalyst (15 mol%) in EtOH at 30 8C for 50 min.
materials and numerous products, the expected product
was obtained in only trace amounts.
Table 2 compares the efficiency of TMG with that of
other reported catalysts in the synthesis of 1,2,3-triazoles
via the reaction of ethyl acetoacatate 1a and 1-azido-4-
nitrobenzene 2a. It is clear from Table 2 that our method is
more efficient for the synthesis of 1,2,3-triazoles deriva-
tives.
According to the optimized conditions, a variety of CH-
acids
1 and azides 2 were employed under similar
We have not established an exact mechanism for the
formation of 3; however, a reasonable possibility is shown
in Scheme 2 [27].
Finally, to further explore the potential of the reaction,
we investigated the reaction of cyclic 1,3-diketones 4 with
azides 2 and obtained bicyclic or tricyclic triazoles 5 in
good isolated yields (Scheme 3).
In conclusion, we have developed a simple and efficient
protocol for the synthesis of 1,2,3-triazoles using TMG as
an organocatalyst under mild reaction conditions.
circumstances to evaluate the substrate scope of the
reaction and 1,2,3-triazoles 3 wereobtained ingood isolated
yields (Table 1). We have shown that these reactions
preceded very cleanly under mild reaction conditions at
30 8C and the use of a wide diversity of CH-acids and aryl
azides in this reaction makes possible the synthesis of
libraries under similar circumstances. However, when
this methodology was investigated by the reaction of CH-
acids with benzyl azide, the TLC and 1H NMR spectra of the
reactions mixture showed
a
combination of starting
Table 1
Synthesis of 1,2,3-triazoles 3.
O
N
TMG (15 mol%)
o
N
R2
N
R1
N3
+
X
EtOH, 30
C
R2
X
R1
1
2
3
Product 3
R1
R2
X
Time (min)
Yield (%)
a
b
c
d
e
f
Me
Me
Ph
CO2Et
CO2Me
CN
4-NO2
4-NO2
4-NO2
4-NO2
4-NO2
3-NO2
3-NO2
3-NO2
3-NO2
4-Cl
50
45
81
77
70
73
77
81
75
71
71
80
76
80
72
68
50
Ph
CO2Et
CO2Et
CO2Et
CO2Me
CN
120
45
4-NO2C6H4
Me
90
g
h
i
Me
90
Ph
90
Ph
CO2Et
CO2Et
CO2Me
CO2Et
CO2Me
CO2Et
160
60
j
Me
k
l
Me
4-Cl
70
Me
4-Me
180
140
180
m
n
Me
4-Me
Me
4-MeO
Please cite this article in press as: Ahmadi F, et al. Efficient TMG catalyzed synthesis of 1,2,3-triazoles. C. R. Chimie
(2013), http://dx.doi.org/10.1016/j.crci.2013.05.006

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3
Scheme 2. Proposed mechanism.
3. Experimental
3.2. Typical procedure for the preparation of 1,2,3-triazoles
3.1. Materials and techniques
A mixture of CH-acid (1 mmol), azide (1 mmol) and
TMG (15 mol%) in EtOH (5 ml) was stirred for an
appropriate time at 30 8C. After completion (TLC), the
solvent was removed under reduced pressure. The residue
was washed with ether (5 mL) and recrystallized from
CHCl3/n-hexane (1:3) to afford the pure product.
The melting points were measured on an Electro-
thermal 9100 apparatus and are uncorrected. 1H and
13C NMR spectra were recorded on a Bruker DRX-300
Avance spectrometer at 300.13 and 75.47 MHz,
respectively. 1H and 13C NMR spectra were obtained
with solutions in DMSO-d6. IR spectra were recorded
using a Bomem MB-Series device. Elemental analyses
3.3. Spectral data
were performed using
a
Heracus CHN-O-Rapid
3.3.1. Ethyl 5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-
4-carboxylate (3a)
analyzer. The chemicals used in this work were obtained
from Fluka and Merck and were used without purifica-
tion.
White powder; yield: 223.76 mg (81%); Mp 181–184 8C.
IR (KBr) (
n
max/cmÀ1): 1725, 1592, 1531, 1434. 1H NMR
O
Ar
N
N
N
TMG
30°C
Ar-N3
/ EtOH
O
O
4
2
5
N3
O
O
N3
OH
4a
2a
O
O
NO2
4b
NO2
NO2
2b
NO2
NO2
NO2
O
O
N
N
O
O
N
N
N
N
N
N
N
N
N
N
O
O
5a
5b
3h (75%)
5c
7h (62%)
5d
7h (60%)
3h (72%)
Scheme 3. Reaction of cyclic 1,3-diketones 4 with azides 2.
Please cite this article in press as: Ahmadi F, et al. Efficient TMG catalyzed synthesis of 1,2,3-triazoles. C. R. Chimie
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3
3
(300 MHz, DMSO-d6):
2.68 (3H, s, CH3), 4.45 (2H, q, 3JHH = 7.1 Hz, OCH2), 7.74 (2H,
d, 3JHH = 8.9 Hz, H–Ar), 8.45 (2H, d, 3JHH = 8.9 Hz, H–Ar). 13
NMR (75 MHz, DMSO-d6): = 10.2, 14.3, 61.3, 125.2, 125.9,
137.4, 138.8, 140.2, 148.1, 161.3. Anal. calcd for
12H12N4O4: C, 52.17; H, 4.38; N, 20.28%. Found: C,
d
= 1.43 (3H, t, JHH = 7.1 Hz, CH3),
3JHH = 7.5 Hz, H–Ar), 8.13 (1H, d, JHH = 7.9 Hz, H–Ar),
8.46–8.52 (2H, m, H–Ar). 13C NMR (75 MHz, DMSO-d6):
d = 10.1, 14.6, 61.0, 112.4, 124.3, 126.8, 137.6, 138.4, 138.8,
140.6, 147.7, 162.1. Anal. calcd for C12H12N4O4: C, 52.17; H,
4.38; N, 20.28%. Found: C, 52.27; H, 4.31; N, 20.34.
C
d
C
52.10; H, 4.32; N, 20.21.
3.3.7. Methyl 5-methyl-1-(3-nitrophenyl)-1H-1,2,3-triazole-
4-carboxylate (3g)
3.3.2. Methyl 5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazole-
4-carboxylate (3b)
White powder; yield: 196.55 mg (75%); Mp 134–135 8C.
IR (KBr) (
(300 MHz, DMSO-d6):
OCH3), 7.94 (1H, t, JHH = 7.3 Hz, H–Ar), 8.11 (1H, d,
3JHH = 7.7 Hz, H–Ar), 8.46–8.52 (2H, m, H–Ar). 13C NMR
n
max/cmÀ1): 1725, 1537, 1527, 1434. 1H NMR
White powder; yield: 201.90 mg (77%); Mp 172–175 8C.
d = 2.55 (3H, s, CH3), 4.35 (3H, s,
3
IR (KBr) (
n
max/cmÀ1): 1732, 1617, 1527, 1501, 1450. 1H
NMR (300 MHz, DMSO-d6):
d
= 2.70 (3H, s, CH3), 4.01 (3H, s,
OCH3), 7.75 (2H, d, JHH = 8.0 Hz, H–Ar), 8.47 (2H, d,
3JHH = 8.0 Hz, H–Ar). 13C NMR (75 MHz, DMSO-d6):
= 10.2,
3
(75 MHz, DMSO-d6):
137.9, 138.1, 138.7, 140.9, 147.8, 161.8. Anal. calcd for
11H10N4O4: C, 50.38; H, 3.84; N, 21.37%. Found: C, 50.26;
d = 9.9, 52.3, 112.7, 124.0, 126.8,
d
52.5, 125.2, 125.8, 137.2, 138.9, 140.1, 148.2, 161.7. Anal.
Calcd for C11H10N4O4: C, 50.38; H, 3.84; N, 21.37%. Found:
C, 50.29; H, 3.89; N, 21.29.
C
H, 3.75; N, 21.44.
3.3.8. 1-(3-Nitrophenyl)-5-phenyl-1H-1,2,3-triazole-4-
carbonitrile (3h)
3.3.3. 1-(4-Nitrophenyl)-5-phenyl-1H-1,2,3-triazole-4-
carbonitrile (3c)
White powder; yield: 206.61 mg (71%); Mp 150–152 8C.
White powder; yield: 203.88 mg (70%); Mp 162–165 8C.
IR (KBr) (
(300 MHz, DMSO-d6):
7.94 (2H, m, H–Ar), 8.42–8.44 (2H, m, H–Ar). 13C NMR
(75 MHz, DMSO-d6): = 110.9, 121.7, 122.3, 125.2, 126.1,
n
max/cmÀ1): 2235, 1604, 1535, 1499. 1H NMR
IR (KBr) (
(300 MHz, DMSO-d6):
7.61 (4H, m, H–Ar), 8.33–8.36 (2H, d, 3JHH = 8.8 Hz, H–Ar).
13C NMR (75 MHz, DMSO-d6):
= 111.4, 121.3, 122.5,
n
max/cmÀ1): 2238, 1597, 1533, 1495. 1H NMR
d = 7.46–7.57 (5H, m, H–Ar), 7.81–
d
= 7.35–7.48 (2H, m, H–Ar), 7.49–
d
d
126.4, 128.1, 130.2, 130.4, 131.8, 139.5, 143.8, 148.0. Anal.
calcd for C15H9N5O2: C, 61.85; H, 3.11; N, 24.04%. Found: C,
61.28; H, 3.06; N, 24.10.
125.2, 125.7, 128.9, 129.8, 131.7, 139.8, 143.4, 148.2. Anal.
calcd for C15H9N5O2: C, 61.85; H, 3.11; N, 24.04%. Found: C,
61.95; H, 3.19; N, 23.98.
3.3.9. Ethyl 1-(3-nitrophenyl)-5-phenyl-1H-1,2,3-triazole-4-
carboxylate (3i)
3.3.4. Ethyl 1-(4-nitrophenyl)-5-phenyl-1H-1,2,3-triazole-4-
carboxylate (3d)
White powder; yield: 239.98 mg (71%); Mp 160–162 8C.
White powder; yield: 246.97 mg (73%); Mp 130–133 8C.
IR (KBr) (
NMR (300 MHz, DMSO-d6):
CH3), 4.24 (2H, q, JHH = 6.9 Hz, OCH2), 7.75–7.85 (5H, m,
n
max/cmÀ1): 1729, 1527, 1347, 1217, 1069. 1H
3
IR (KBr) (
n
max/cmÀ1): 1712, 1528, 1347, 1224, 1105. 1H
d
= 1.16 (3H, t, JHH = 6.9 Hz,
3
NMR (300 MHz, DMSO-d6):
d
= 2.58 (3H, bs, CH3), 5.41 (2H,
bs, OCH2), 7.37–7.50 (5H, m, H–Ar), 7.98 (2H, d,
H–Ar), 8.25–8.28 (2H, m, H–Ar), 8.35–8.39 (2H, m, H–Ar).
13C NMR (75 MHz, DMSO-d6):
d = 14.2, 61.4, 121.6, 123.6,
3
3JHH = 8.2 Hz, H–Ar), 8.48 (2H, d, JHH = 8.2 Hz, H–Ar). 13C
NMR (75 MHz, DMSO-d6):
d
= 10.3, 66.5, 125.5, 127.0,
125.4, 130.2, 131.6, 132.4, 132.6, 136.0, 137.3, 140.1, 148.3,
148.6, 160.3. Anal. calcd for C17H14N4O4: C, 60.35; H, 4.17;
N, 16.56%. Found: C, 60.26; H, 4.12; N, 16.49.
128.7, 128.8, 129.0, 136.2, 136.4, 140.3, 140.6, 148.3, 161.2.
Anal. calcd for C17H14N4O4: C, 60.35; H, 4.17; N, 16.56%.
Found: 60.28; H, 4.12; N, 16.49.
3.3.10. Ethyl 1-(4-chlorophenyl)-5-methyl-1H-1,2,3-
triazole-4-carboxylate (3j)
3.3.5. Ethyl 1,5-bis(4-nitrophenyl)-1H-1,2,3-triazole-4-
carboxylate (3e)
White powder; yield: 212.0 mg (80%); Mp 155–158 8C.
White powder; yield: 295.15 mg (77%); Mp 159–162 8C.
IR (KBr) (
1H NMR (300 MHz, DMSO-d6):
CH3), 2.52 (3H, s, CH3), 4.38 (2H, q, JHH = 7.0 Hz, OCH2),
7.61–7.70 (4H, m, H–Ar). 13C NMR (75 MHz, DMSO-d6):
n
max/cmÀ1): 1715, 1566, 1498, 1421, 1244, 1106.
IR (KBr) (
NMR (300 MHz, DMSO-d6):
n
max/cmÀ1): 1724, 1525, 1347, 1222, 1075. 1H
d
= 1.36 (3H, t, 3JHH = 7.0 Hz,
3
3
d
= 1.16 (3H, t, JHH = 6.9 Hz,
3
CH3), 4.24 (2H, q, JHH = 6.9 Hz, OCH2), 7.69 (2H, d,
3JHH = 8.5 Hz, H–Ar), 7.75 (2H, d, JHH = 8.2 Hz, H–Ar),
d = 10.1, 14.6, 60.95, 127.7, 130.2, 134.3, 135.3, 136.3,
139.9, 161.4. Anal. calcd for C12H12ClN3O2: C, 54.25; H,
4.55; N, 15.82%. Found: C, 54.34; H, 4.61; N, 15.77.
3
8.28 (2H, d, 3JHH = 8.2 Hz, H–Ar), 8.34 (2H, d, 3JHH = 8.5 Hz,
H–Ar). 13C NMR (75 MHz, DMSO-d6):
d = 14.2, 61.4, 123.7,
125.4, 127.5, 132.4, 132.6, 137.5, 139.9, 140.1, 148.2, 148.7,
160.3. Anal. calcd for C17H13N5O6: 53.27; H, 3.42; N,
18.27%. Found: C, 53.14; H, 3.50; N, 18.35.
3.3.11. Methyl 1-(4-chlorophenyl)-5-methyl-1H-1,2,3-
triazole-4-carboxylate (3k)
White powder; yield: 190.76 mg (76%); Mp 171–173 8C.
3.3.6. Ethyl 5-methyl-1-(3-nitrophenyl)-1H-1,2,3-triazole-
4-carboxylate (3f)
IR (KBr) (
NMR (300 MHz, DMSO-d6):
OCH3), 7.63–7.72 (4H, m, H–Ar). 13C NMR (75 MHz, DMSO-
d6): = 10.1, 52.2, 127.7, 130.2, 134.3, 135.2, 136.1, 140.0,
161.9. Anal. calcd for C11H10ClN3O2: C, 52.50; H, 4.01; N,
16.70%. Found: C, 52.56; H, 3.97; N, 16.64.
n
max/cmÀ1): 1724, 1566, 1437, 1248, 1110. 1H
d
= 2.50 (3H, s, CH3), 3.90 (3H, s,
White powder; yield: 218.23 mg (81%); Mp 144–146 8C.
IR (KBr) (
DMSO-d6):
n
max/cmÀ1): 1724, 1537, 1425. 1H NMR (300 MHz,
d
3
d
= 1.34 (3H, t, JHH = 7.4 Hz, CH3), 2.56 (3H, s,
3
CH3), 4.37 (2H, q, JHH = 7.4 Hz, OCH2), 7.95 (1H, t,
Please cite this article in press as: Ahmadi F, et al. Efficient TMG catalyzed synthesis of 1,2,3-triazoles. C. R. Chimie
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3.3.12. Ethyl 5-methyl-1-(p-tolyl)-1H-1,2,3-triazole-4-
carboxylate (3l)
(300 MHz, DMSO-d6):
CH2), 3.10 (2H, s, CH2), 8.04 (2H, d, JHH = 8.5 Hz, H–Ar),
8.49 (2H, d, 3JHH = 8.5 Hz, H–Ar). 13C NMR (75 MHz, DMSO-
d6): d = 28.0, 34.6, 36.0, 52.2, 124.9, 125.8, 140.4, 142.1,
145.6, 147.9, 190.1. Anal. calcd for C14H14N4O3: C, 58.73; H,
4.93; N, 19.57%. Found: C, 58.65; H, 4.85; N, 19.52.
d
= 1.06 (6H, s, 2 CH3), 2.52 (2H, s,
3
White powder; yield: 196.0 mg (80%); Mp 136–138 8C.
IR (KBr) (
NMR (300 MHz, DMSO-d6):
n
max/cmÀ1): 1711, 1515, 1429, 1239, 1107. 1H
3
d
= 1.33 (3H, t, JHH = 7.0 Hz,
CH3), 2.42 (3H, s, CH3), 2.50 (3H, s, CH3), 4.35 (2H, q,
3JHH = 7.0 Hz, OCH2), 7.44 (2H, d, 3JHH = 8.1 Hz, H–Ar), 7.50
(2H, d, 3JHH = 8.1 Hz, H–Ar). 13C NMR (75 MHz, DMSO-d6):
3.3.18. 6,6-Dimethyl-1-(3-nitrophenyl)-6,7-dihydro-1H-
benzo[d][1,2,3]triazol-4(5H)-one (5d)
d
= 10.1, 14.6, 21.21, 60.8, 125.7, 130.5, 133.1, 136.1, 139.7,
140.4, 161.5. Anal. calcd for C13H15N3O2: C, 63.66; H, 6.16;
N, 17.13%. Found: C, 63.60; H, 6.23; N, 17.20.
Cream powder; yield: 171.60 mg (60%); Mp 204–206 8C.
IR (KBr) (
DMSO-d6):
n
max/cmÀ1): 1694, 1598, 1513. 1H NMR (300 MHz,
d
= 1.06 (6H, s, 2 CH3), 2.50 (2H, overlap with
3.3.13. Methyl 5-methyl-1-(p-tolyl)-1H-1,2,3-triazole-4-
carboxylate (3m)
solvent, CH2), 3.06 (2H, s, CH2), 7.94–7.99 (1H, m, H–Ar),
8.18–8.21(1H,m,H–Ar), 8.44–8.47(1H,d,H–Ar), 8.53(1H,s,
White powder; yield: 166.32 mg (72%); Mp 133–135 8C.
H–Ar). 13C NMR (75 MHz, DMSO-d6):
d = 28.1, 34.2, 36.0,
IR (KBr) (
n
max/cmÀ1): 1709, 1523, 1421, 1248. 1H NMR
52.3, 119.2, 124.8, 130.4, 132.0, 136.3, 143.3, 145.8, 148.8,
190.2. Anal. Calcd for C14H14N4O3: C, 58.73; H, 4.93; N,
19.57%. Found: C, 58.83; H, 4.99; N, 19.50.
(300 MHz, DMSO-d6):
CH3), 4.31 (3H, s, OCH3), 7.37 (2H, d, JHH = 7.8 Hz, H–Ar),
7.51 (2H, d, 3JHH = 7.8 Hz, H–Ar). 13C NMR (75 MHz, DMSO-
d
= 2.40 (3H, s, CH3), 2.53 (3H, s,
3
d6): d = 14.1, 21.30, 61.3, 125.7, 130.2, 133.4, 135.7, 139.6,
Acknowledgements
140.7, 161.0. Anal. Calcd for C12H13N3O2: C, 62.33; H, 5.67;
N, 18.17%. Found: C, 62.25; H, 5.72; N, 18.11.
We gratefully acknowledge financial support from the
Research Council of Shahid Beheshti University.
3.3.14. Ethyl 1-(4-methoxyphenyl)-5-methyl-1H-1,2,3-
triazole-4-carboxylate (3n)
References
White powder; yield: 177.48 mg (68%); Mp 137–139 8C.
max/cmÀ1): 1712, 1513, 1248. 1H NMR (300 MHz,
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IR (KBr) (
DMSO-d6):
n
3
d
= 1.46 (3H, t, JHH = 7.2 Hz, CH3), 2.56 (3H, s,
3
CH3), 3.89 (3H, s, OCH3), 4.47 (2H, q, JHH = 7.2 Hz, OCH2),
7.06 (2H, d, JHH = 7.9 Hz, H–Ar), 7.35 (2H, d, JHH = 7.9 Hz,
H–Ar). 13C NMR (75 MHz, DMSO-d6):
= 9.9, 14.7, 54.1,
3
3
d
60.9, 120.4, 129.5, 134.1, 135.6, 140.0, 143.2, 161.1. Anal.
calcd for C13H15N3O2: C, 59.76; H, 5.79; N, 16.08%. Found:
C, 59.69; H, 5.74; N, 16.13.
3.3.15. 1-(4-Nitrophenyl)-1H-naphtho[2,3-d][1,2,3]triazole-
4,9-dione (5a)
White powder; yield: 230.40 mg (72%); Mp 264–266 8C.
IR (KBr) (
(300 MHz, DMSO-d6):
d, 3JHH = 8.4 Hz, H–Ar), 8.25–8.27 (2H, m, H–Ar), 8.53 (2H, d,
3JHH = 8.4 Hz,H–Ar). 13C NMR (75 MHz, DMSO-d6):
= 124.7,
n
max/cmÀ1): 2917, 1658, 1561, 1507. 1H NMR
d
= 7.94–8.02 (2H, m, H–Ar), 8.15 (2H,
d
125.1, 127.2, 127.4, 127.5, 133.0, 133.7, 135.3, 135.6, 140.2,
145.4, 148.8, 174.4, 177.4. Anal. calcd for C16H8N4O4: C,
60.00; H, 2.52; N, 17.49%. Found: C, 59.95; H, 2.47; N, 17.41.
3.3.16. 1-(3-Nitrophenyl)-1H-naphtho[2,3-d][1,2,3]triazole-
4,9-dione (5b)
Orange powder; yield: 240.0 mg (75%); Mp 238–240 8C.
IR (KBr) (
(300 MHz, DMSO-d6):
8.28 (2H, m, H–Ar), 8.55 (1H, bs, H–Ar), 8.78 (1H, bs, H–Ar).
13C NMR (75 MHz, DMSO-d6):
= 121.2, 125.8, 127.4, 127.6,
n
max/cmÀ1): 2917, 1658, 1561, 1507. 1H NMR
d
= 7.97–8.15 (4H, m, H–Ar), 8.25–
d
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Lett. 51 (2010) 5385.
131.4, 132.3, 132.4, 133.1, 133.4, 135.3, 135.6, 136.2, 147.5,
148.2, 174.5, 177.4. Anal. calcd for C16H8N4O4: C, 60.00; H,
2.52; N, 17.49%. Found: C, 59.91; H, 2.59; N, 17.43.
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12917.
3.3.17. 6,6-Dimethyl-1-(4-nitrophenyl)-6,7-dihydro-1H-
benzo[d][1,2,3]triazol-4(5H)-one (5c)
Cream powder; yield: 177.32 mg (62%); Mp 267–
269 8C. IR (KBr) (
n
max/cmÀ1): 1694, 1598, 1513. 1H NMR
[27] L.J.T. Danence,Y.Gao,M.Li,Y.Huang,Wang,J.Chem.Eur.J.17(2011)3584.
Please cite this article in press as: Ahmadi F, et al. Efficient TMG catalyzed synthesis of 1,2,3-triazoles. C. R. Chimie
(2013), http://dx.doi.org/10.1016/j.crci.2013.05.006