Rapid, green, and catalyst-free one-pot three-component syntheses of 5-substituted 1H-tetrazoles in magnetized water

Article abstract of DOI:10.1007/s13738-017-1193-y

The catalyst-free multi-component reactions of aldehydes, malononitrile, and sodium azide at a relatively low temperature in magnetized water provided 5-substituted 1H-tetrazoles in high-to-excellent yields. This method offers the advantages of short reac

Full text of DOI:10.1007/s13738-017-1193-y

J IRAN CHEM SOC
DOI 10.1007/s13738-017-1193-y
ORIGINAL PAPER
Rapid, green, and catalyst‑free one‑pot three‑component
syntheses of 5‑substituted 1H‑tetrazoles in magnetized water
Mohammad Bakherad1 · Rahele Doosti1 · Ali Keivanloo1 · Mostafa Gholizadeh2 ·
Khosrow Jadidi3
Received: 6 March 2017 / Accepted: 12 September 2017
© Iranian Chemical Society 2017
Abstract The catalyst-free multi-component reactions of
aldehydes, malononitrile, and sodium azide at a relatively
low temperature in magnetized water provided 5-substituted
1H-tetrazoles in high-to-excellent yields. This method ofers
the advantages of short reaction times, low costs, quantita-
tive reaction yields, simple work-up, green, and no need for
any organic solvent.
5-substituted 1H-tetrazoles. A known procedure for the syn-
thesis of 5-substituted 1H-tetrazoles involves treatment of
primary amines with ortho- carboxylic acid ester/sodium
azide and employment of metallic trifates or imidazolium
ionic liquids [5–7]. However, a lot of these protocols have
some drawbacks like the use of toxic metals, strong Lewis
acids, and expensive reagents, low product yield, drastic
reaction conditions, and presence of hydrazoic acid that is
toxic and explosive. Moreover, all of the known methods
use organic solvents, specifcally the dipolar aprotic ones
like DMF [8]. Therefore, the development of a suitable and
safe process for the synthesis of new tetrazole derivatives is
an appealing goal for investigation.
Keywords Magnetized water · Catalyst-free · Green
method · 5-Substituted 1H-tetrazoles
Introduction
The design and exploration of novel catalyst-free meth-
ods for pharmacological agents in aqueous media is an ideal
option and a major challenge for chemists to reduce the eco-
logical problems and economic burdens [9]. In this context,
domino multi-component reactions (MCRs), which can take
place in aqueous media, have been considerably followed in
the past few years because of their efective atom economy
and green characteristics [10]. These reactions are efcient
in preparing highly-functionalized small organic molecules
from readily-available starting materials in one step with
inherent fexibility for producing molecular diversity and
complexity coupled with minimization of cost, time, labor,
and waste production [11]. Moreover, these reactions fre-
quently yield excellent regio- and chemo-selectivities [12].
Among the commonly-used solvents in organic synthe-
sis, water is quite non-toxic, and it is the most economical,
most abundant, safest, and most environmentally friendly
medium. Sometimes water shows a higher reactivity and
selectivity in comparison with the other conventional
organic solvents because of its strong hydrogen-bonding
ability [13]. These characteristics allow water to act as a
solvent, a reactant or a catalyst, which is diferent from
Attention to tetrazole chemistry has increased in the recent
years, chiefy as a consequence of the role played by this
heterocyclic functionality in medicinal chemistry as a met-
abolically-stable alternative for carboxylic acid functionali-
ties [1]. Further signifcant applications of tetrazoles can be
found in materials science, coordination chemistry, and as
intermediates in a range of synthetic transformations [2–4].
Various methods have been developed for the synthesis of
Electronic supplementary material The online version of this
article (doi:10.1007/s13738-017-1193-y) contains supplementary
material, which is available to authorized users.
* Mohammad Bakherad
m.bakherad@yahoo.com
1
School of Chemistry, Shahrood University of Technology,
Shahrood 3619995161, Iran
2
Department of Chemistry, Ferdowsi University of Mashhad,
Mashhad 91779, Iran
3
Department of Chemistry, Shahid Beheshti University,
Tehran 1983963113, Iran
Vol.:(0123456789)
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J IRAN CHEM SOC
those spotted in the conventional organic solvents. Since the
innovative studies carried out on the Diels–Alder reactions
by Breslow [14], there has been a growing realization that
organic reactions can go ahead well in aqueous media and
suggest benefts over those taking place in organic solvents
[15]. However, most chemical reactions could not be per-
formed in water, as a solvent, since they need the presence
of reagents, catalysts or energy.
we attempted to carry out the catalyst-free synthesis of
5-substituted 1H-tetrazoles 4 using magnetized water, as a
solvent, which helped to lower the reaction time and increase
the yield of the target product.
Magnetized water was prepared using a static mag-
netic system of 6000 G [26] feld strength with a fow rate
of 500 mL s−1 at diferent magnetic feld time exposures
(Fig. 1). Moreover, doubly distilled water, which was deion-
ized by a Millipore Q-Plus 185 system, was used in the
experiments.
From the 1950s, we have known that water can be mag-
netized when exposed to a magnetic feld, although the efect
is very small [16–18]. Based on the literature surveys car-
ried out on magnetized water during the last few years, most
researchers have been interested in studying the magnetic
feld efects on the properties of water [19, 20], especially
the hydrogen bond distribution [21, 22]. On the other hand,
various researchers have studied the efects of magnetized
water on the morphology of precipitated calcium carbonate
[23], TiO2-based varistors [24], and synthesis of manganese
oxide nano-crystals [25]. Recently, we have reported the
synthesis of pyrano[2,3-c]pyrazoles and pyrano[4′,3′:5,6]
pyrazolo[2,3-d]pyrimidines in magnetized water, as a green
solvent [26]. Herein, we wish to report, for the frst time, a
catalyst-free, rapid, simple, and green synthetic method for
the synthesis of 5-substituted 1H-tetrazoles via the one-pot
multi-component reaction (MCR) of aldehydes, malononi-
trile, and sodium azide in magnetized water (Scheme 1).
Our extensive literature survey showed that there are only
a few reports related to the synthesis of (E)-(1H-tetrazole-
5-yl) acrylonitrile derivatives 4 using a three-component
domino reaction of an aldehyde, malononitrile, and sodium
azide [27–32]. Safaei-Ghomi et al. [31] have reported
that this transformation can be completed in the presence
of 6 mol% of NiO nanoparticles in DMF at 70 °C for 6 h.
Although this method was quite useful, it had some limita-
tions such as the use of catalyst and organic solvent, long
reaction time, and harsh reaction conditions. Also, Dabiri
et al. have describes the catalyst-free synthesis of 5-substi-
tuted 1H-tetrazoles 4 with 63–81% product yield in water at
50 °C for 24–31 h [32]. In this method, Dabiri et al. found
that water was the best solvent with respect to the reaction
yield, which could be ascribed to the existence of power-
ful hydrogen bond interactions at the organic phase-water
interface, which stabilizes the reaction intermediate [33].
Therefore, according to the results obtained by Dabiri et al.,
Initially, we used the three-component reaction of ben-
zaldehyde 1a, malononitrile 2, and sodium azide 3 as a
model reaction to explore the suitable reaction conditions.
As indicated in Table 1 (entries 1–3), the magnetization time
plays a critical role in obtaining a high-yield product 4a.
The best product yield 4a was found in water magnetized in
5 min and for a reaction time of 15 min at 40 °C (Table 1,
entry 2). Dabiri et al. reported that this transformation could
be completed in water at 50 °C for 24 h [28]. During the
optimization process, the reaction temperature was varied
between 25 and 60 °C, with 40 °C giving the optimal reac-
tion enhancement. Moreover, to demonstrate the efciency
and practicability of this method in the synthesis of these
types of molecules, the model reaction was carried out in a
scale of 50 mmol. As expected, the desired product could
be obtained with 96% yield in 15 min (Table 1, entry 6).
We performed the model reaction using with 2 equivalent
of sodium azide. Increasing of amount of sodium azide did
not improve the product yield (Table 1, entry 7). Also the
above three-component reaction was carried out in doubly
distilled water to establish the real efcacy of magnetized
water. As shown in Table 1, only a low product yield was
obtained even after the reaction time was prolonged to 2 h
(Table 1, entry 8).
A number of researchers have reported that when the
applied magnetic feld is removed from the magnetized
water, its magnetization efect does not disappear immedi-
ately, and can be maintained for a relatively long period of
N
N
H
N
NC
Ar
Ar
CN
magnetized water
40 oC
N
H
O
+
+
NaN3
H
CN
Scheme 1 Synthesis of 5-substituted 1H-tetrazoles in magnetized
Fig. 1 Pilot for solvent magnetizing apparatus
water
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J IRAN CHEM SOC
Table 1 Synthesis of (E)-3-
phenyl-2-(1H-tetrazole-5-yl)
acrylonitrile 4a under various
conditions
Entry
Solvent
Magnetization time (min)
Temp. (°C)
Reaction
Yield (%)a
time (min)
1
2
3
4
5
6
7
8
Magnetized water
Magnetized water
Magnetized water
Magnetized water
Magnetized water
Magnetized water
Magnetized water
Doubly distilled water
2
5
10
5
5
5
5
40
40
40
60
25
40
40
40
60
15
15
15
120
15
80
97
97
97
60
96b
97c
20
15
120
Non-magnetized
Reaction conditions: benzaldehyde (1.0 mmol), malononitrile (1.0 mmol), sodium azide (1.0 mmol), sol-
vent (4 mL)
a Isolated yield
b50 mmol scale
c2 mmol of NaN3
Table 2 Synthesis of (E)-3-phenyl-2-(1H-tetrazole-5-yl) acrylonitrile
4a at diferent times after water magnetization
(Table 3). The details of the stereo-chemical structure deter-
mination have been described earlier by Dabiri and cowork-
ers [32]. As shown in Table 3, aromatic aldehydes having
electron-withdrawing groups reacted at faster rates com-
pared with those having electron-releasing groups. Since
no acid or metal-containing catalysts were used, our sys-
tem allowed the use of acid-labile substrates. For example,
4-N,N-dimethyl amino benzaldehyde, which tends to poison
acids or metal-containing species by means of acid–base
interaction or coordination, can be converted to the desired
product in high yields without damage to the tertiary amine
group (Table 3, entry 5). Furthermore, furfural, which is
known as an acid-sensitive species, was also proved to be
applicable in magnetized water (Table 3, entry 13), indicat-
ing the usefulness of our methodology.
Entry
Time after completion of magnetic
exposure (h)
Yield (%)a
1
2
3
4
5
6
0 (freshly-magnetized water)
2
4
6
8
10
97
97
95
85
70
50
Reaction conditions: aldehyde (1.0 mmol), malononitrile (1.0 mmol),
sodium azide (1.0 mmol), magnetized water (4 mL), magnetization
time (5 min), reaction time (15 min), 40 °C
a Isolated yield
Notably, at the beginning of the reactions, a solution that
seemed to be transparent was observed because aldehydes,
malononitrile, and sodium azide were soluble in magnetized
water. The latter formed a product, which was found to be
insoluble in magnetized water. At the end of the reaction,
a large amount of a solid product was formed. This made
stirring of the reaction mixture difcult.
time. This phenomenon is referred to as the “memory efect”
of magnetized water, i.e. how long water magnetization
efect remains after completion of the magnetic exposure
[34]. Therefore, we examined the memory efect of magnet-
ized water. The model reaction was performed in magnetized
water at diferent times after completion of the magnetic
exposure. After a magnetic exposure of 5 min, magnetized
water was left standing for diferent time periods. It was
found that magnetized water kept its magnetization property
for up to 4 h, and a reaction performed in water magnet-
ized for some time was as acceptable as that carried out
in a freshly-magnetized water with a high reaction yield
(Table 2).
As mentioned earlier, applying a magnetic feld to water
causes several changes in it, one of which is a change in
the hydrogen bond distribution in magnetized water com-
pared with that for normal water. The characteristic prop-
erties of water are chiefy due to its 3D hydrogen bonding
network. An external magnetic feld can weaken or even
partly break the inter-molecular hydrogen bonds in water,
and thus increase the number of monomer water molecules,
which may result in some biological efects [35–38]. Yin
et al. have shown that weakening of the hydrogen bonds
and the Van der Waals forces between water molecules in
magnetized water contribute to the amount of its evaporation
[39]. Nakagawa et al. have examined the efect of magnetic
Following our study to synthesize 5-substituted 1H-tetra-
zoles via a multi-component Knoevenagel condensation/1,3-
dipolar cycloaddition reaction, the best conditions (Table 1,
entry 2) were applied to various aromatic aldehydes and het-
ero-aromatics to give the related (E)-(1H-tetrazol-5-yl)acry-
lonitriles 4 in high-to-excellent yields and stereo-selectivity
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J IRAN CHEM SOC
M.p. (°C) Lit. [ref.]
Table 3 Synthesis of
Entry
Ar
Product
Time (min)
Yield (%)
5-substituted 1H-tetrazoles 4
1
2
3
4
5
6
7
8
Ph
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
4o
15
15
15
20
20
20
20
10
10
10
10
10
20
20
25
97
95
90
93
95
90
93
97
91
93
97
98
92
94
90
167–168 (168–170) [32]
159–161 (159–161) [32]
158–159
150–151 (153–155) [31]
171–172
157–158
95–96
160–161 (165–167) [32]
142–143
132–133
97–98
163–164 (166–168) [32]
253–254
4-OH–C6H4
4-Me–C6H4
4-MeO–C6H4
4-Me2N–C6H4
3,5-(OMe)2–4-OH–C6H2
2,3,4-(OMe)3–C6H2
4-Br–C6H4
2,4-Cl2C6H3
2-NO2–C6H4
3-NO2–C6H4
4-NO2–C6H4
2′-Furanyl
2′-thiophenyl
2′-Pyridinyl
9
10
11
12
13
14
15
85–86
185–186
Reaction conditions: Aldehyde (1.0 mmol), malononitrile (1.0 mmol), sodium azide (1.0 mmol), magneti-
zation time (5 min), magnetized water (4 mL), at 40 °C
Isolated yield
feld on water vaporization. They have found that the applied
magnetic feld enhances water vaporization into the air [40].
Moreover, Toledo et al. have proved the efect of an external
magnetic feld on the physical and chemical properties of
water through an experimental procedure and a theoretical
one. They have found that an external magnetic feld infu-
ences the hydrogen bond networks. They have pointed out
the existence of a competition between the intra- and inter-
molecular hydrogen bond networks in water, which weak-
ens the stronger intra-cluster hydrogen bonds, breaks the
larger clusters, and forms the smaller ones with the stronger
inter-cluster hydrogen bonds [41]. Therefore, the number of
hydrogen bonds between the magnetized water molecules
and the reacting molecules increases. Thus we think that
the hydrogen bonds between the molecules of magnetized
water and the molecules of the substrates and intermedi-
ates involved in a reaction are responsible for the reaction
activation.
the present article demonstrate that the present protocol is
indeed superior to several of the other protocols. As shown
in Table 4, most of the listed methodologies sufer from
some limitations such as use of catalysts, elevated tempera-
tures and the prolonged reaction times.
Conclusion
A novel, efficient, catalyst-free, green, and convenient
method was proposed for the one-pot three-component syn-
thesis of 5-substituted 1H-tetrazoles in magnetized water.
This method not only ofers substantial improvements in the
reaction rates and yields but also avoids the use of catalysts
or solvents. In addition, the promising points for the pre-
sented methodology are its efciency, generality, high yield,
short reaction time, clean reaction profle, simple work-up
procedure, and fnally, agreement with the green chemis-
try protocols, making it a useful and attractive process for
the synthesis of 5-substituted 1H-tetrazoles. This protocol
employs magnetized water as an inherently-safe and a low-
cost reaction medium in organic synthesis. Moreover, the
presented method can be used in large-scale syntheses.
A plausible mechanism for the synthesis of 5-substituted
1H-tetrazole 4a from benzaldehyde 1a, malononitrile 2, and
sodium azide 3, is shown in Scheme 2. Magnetized water
plays a major role in its promoting activity for the forma-
tion of intermediate (I), which is readily prepared in situ
by the Knoevenagel condensation of benzaldehyde 1a with
the highly active CH acidic malononitrile 2. Finally, the
1,3-dipolar cycloaddition reaction between the C≡ N group
of phenylidenemalononitrile and azide ion followed by tau-
tomerization yielded 5-substituted 1H-tetrazole 4a.
Experimental
Aldehydes, malononitrile, and sodium azide were pur-
chased from Merck, Fluka or Aldrich. Melting points were
determined using an electro-thermal C14500 apparatus. All
the known compounds were identifed by comparing their
A comparative study of the reaction conditions for the
synthesis of (E)-3-phenyl-2-(1H-tetrazole-5-yl) acryloni-
trile 4a using the methods given in Table 4 and reported in
1 3

J IRAN CHEM SOC
Scheme 2 Plausible mecha-
nism for synthesis of (E)-
3-phenyl-2-(1H-tetrazole-5-yl)
acrylonitrile 4a
H
H
O
H
O
H
H
H
O
O
H
H
H
H
H
H
O
O
H
H
CN
H
O
HO
CN
+
H
NC
CN
Ph
H
-H2O
Ph
C
N
Ph
CN
N
N
N Na
(I)
Na
H
H
N
O
N
N
N
N
HN
N
H
N
H
Ph
CN
Ph
CN
4a
(II)
Table 4 Comparison of
reaction conditions of
Entry
Catalyst
Solvent
Temp (°C)
Time
Yeild (%)
References
magnetized water with the most
recent reported catalyst for the
synthesis of (E)-3-phenyl-2-
(1H-tetrazole-5-yl) acrylonitrile
4a
1
2
3
4
5
6
[BMIM]N3
SMA/Microwaves
ZrP2O7
Nano-NiO
Catalyst-free
Catalyst-free
–
100
50
70
70
50
40
10 h
15 min
6 h
6 h
24 h
80
93
91
90
81
97
[1]
[2]
[5]
[4]
[3]
H2O
DMF
DMF
H2O
Magnetized water
15 min
Present work
melting points and 1H NMR data with those in the authen-
tic samples. 1NMR spectra were recorded on a Bruker 300
(300 MHz 1H, 75 MHz 13C) spectrometer. 1H NMR signals
were reported relative to Me4Si (δ 0.0) or residual CHCl3
(δ 7.26). 13C NMR signals were reported relative to CDCl3
(δ 77.16). Multiplicities were described using the follow-
ing abbreviations: s = singlet, d = doublet, t = triplet, and
m = multiplet.
General procedure for synthesis of (E)‑(1H‑tetra‑
zol‑5‑yl)acrylonitrile derivatives (4a–o)
To a 10-mL round-bottomed fask equipped with a mag-
netic stirrer bar and containing magnetized water (4 mL,
with magnetization time of 5 min), were added an alde-
hyde (1.0 mmol), malononitrile (1.0 mmol, 0.067 g), and
sodium azide (1.0 mmol, 0.065 g). The reaction mixture
was stirred at 40 °C, and the reaction progress was moni-
tored by TLC using chloroform as the eluent. After com-
pletion of the reaction, the precipitate formed was fltered
and purifed by recrystallization from ethanol to aford the
desired product (Table 3).
Preparation of magnetized water
A magnetic treatment apparatus was assembled as shown in
Fig. 1. This apparatus is equipped with a powerful magnet
6000 G. A centrifugal pump was used to circulate water in
the system. Water was treated in the system for 5 min, and
then 100 mL of this magnetized water was used in the cur-
rent work.
1 3

J IRAN CHEM SOC
(E)‑3‑(4‑Methylphenyl)‑2‑(1H‑tetrazole‑5‑yl) acryloni‑
C10H5Cl2N5: C: 45.14; H: 1.89; N: 26.32; found: C: 45.32;
H: 1.98; N: 26.15.
trile (4c)
M.p., 158–159 °C; 1H NMR (300 MHz, CDCl3): δ 2.44 (s,
3H,CH3), 7.3 (d, J = 8.1 Hz, 2H, Ar), 7.70 (s, 1H, CH),
7.78 (d, J = 8.1 Hz, 2H, Ar–H) ppm; 13C NMR (75 MHz,
CDCl3): δ 22.0, 81.2, 112.8, 114.0, 128.4, 130.4, 130.9,
146.4, 159.7 ppm; Anal. Calcd. for C11H9N5: C: 62.55; H:
4.29; N: 33.16; found: C: 62.68; H: 4.37; N: 33.29.
(E)‑3‑(2‑Nitroyphenyl)‑2‑(1H‑tetrazole‑5‑yl) acryloni‑
trile (4j)
M.p., 132–133 °C; 1H NMR (300 MHz, CDCl3): δ 7.76–7.89
(m, 3H, Ar), 8.31 (d, J = 7.8 Hz, 1H, Ar), 8.43 (s, 1H, CH)
ppm; 13C NMR (75 MHz, CDCl3): δ 88.5, 111.0, 112.2,
125.8, 126.7, 130.5, 133.4, 135.0, 146.8, 158.9 ppm; Anal.
Calcd. for C10H6N6O2: C: 49.59; H: 2.50; N: 34.70; found:
C: 49.73; H: 2.60; N: 34.88.
(E)‑3‑(4‑N,N‑dimethylaminophenyl)‑2‑(1H‑tetra‑
zole‑5‑yl) acrylonitrile (4e)
(E)‑3‑(3‑Nitroyphenyl)‑2‑(1H‑tetrazole‑5‑yl) acryloni‑
M.p., 171–172 °C; 1H NMR (300 MHz, CDCl3): δ 3.12 (s,
6H, CH3), 6.64 (d, J = 9.0 Hz, 2H, Ar), 7.39 (s, 1H, CH),
7.74 (d, J = 9.0 Hz, 2H, Ar) ppm; 13C NMR (75 MHz,
CDCl3): δ 40.2, 71.6, 111.6, 115.0, 116.0, 119.2, 133.8,
154.2, 158.0 ppm; Anal. Calcd. for C12H9N6: C: 59.99; H:
5.03; N: 34.98; found: C: 60.12; H: 5.13; N: 34.86.
trile (4k)
1
M.p., 97–98 °C; H NMR (300 MHz, CDCl3): δ 7.77 (t,
J = 8.1 Hz, 1H, Ar), 7.89 (s, 1H, CH), 8.31 (s, 1H, CH),
8.45 (dd, J = 8.1, 1.2 Hz, 1H, Ar), 8.64 (s, 1H, Ar) ppm; 13
C
NMR (75 MHz, CDCl3): δ 86.7, 111.6, 112.7, 125.5, 128.2,
131.0, 132.0, 134.9, 148.6, 157.0 ppm; Anal. Calcd. for
C10H6N6O2: C: 49.59; H: 2.50; N: 34.70; found: C: 49.77;
H: 2.41; N: 34.85.
(E)‑3‑(3,5‑Dimethoxy‑4‑hydroxyphenyl)‑2‑(1H‑tetra‑
zole‑5‑yl) acrylonitrile (4f)
(E)‑3‑(2‑Furanyl)‑2‑(1H‑tetrazole‑5‑yl) acrylonitrile
1
M.p., 157–158 °C; H NMR (300 MHz, CDCl3): δ 3.91
(4m)
(s, 6H,OCH3), 6.42 (br, 1H, OH), 7.19 (s, 1H, Ar), 7.23
(s, 1H, Ar), 7.59 (s, 1H, CH) ppm; 13C NMR (75 MHz,
CDCl3): δ 56.5, 78.4, 109.3, 113.6, 114.3, 122.7, 141.5,
147.3, 159.4 ppm; Anal. Calcd. for C12H11N5O3: C: 52.75;
H: 4.06; N: 25.63; found: C: 52.62; H: 4.17; N: 25.80.
M.p., 253–254 °C; 1H NMR (300 MHz, CDCl3): δ 6.68–6.70
(m, 1H, furan), 7.32 (d, J = 3.9 Hz, 1H, furan), 7.49 (s,
1H, CH), 7.78 (d, J = 1.8, Hz, 1H, furan) ppm; 13C NMR
(75 MHz, CDCl3): δ 112.6, 113.8, 114.4, 123.5, 130.9,
143.1, 148.1, 149.6 ppm; Anal. Calcd. for C8H5N5O: C:
51.34; H: 2.69; N: 37.42; found: C: 51.20; H: 2.57; N: 37.58.
(E)‑3‑(2,3,4‑Trimethoxyphenyl)‑2‑(1H‑tetrazole‑5‑yl)
acrylonitrile (4g)
(E)‑3‑(2‑Thiophenyl)‑2‑(1H‑tetrazole‑5‑yl) acrylonitrile
1
(4n)
M.p., 95–96 °C; H NMR (300 MHz, CDCl3): δ 3.84
(s, 3H,OCH3), 3.95 (s, 3H,OCH3), 3.98 (s, 3H,OCH3),
6.75 (d, J = 9.3 Hz, 1H, Ar), 8.06 (s, 1H, CH), 8.10 (d,
J = 9.3 Hz, 1H, Ar) ppm; 13C NMR (75 MHz, CDCl3):
δ 56.4, 61.0, 62.1, 78.7, 107.8, 113.5, 114.8, 118.2,
124.7, 141.7, 153.6, 154.5, 159.7 ppm; Anal. Calcd. for
C13H13N5O3: C: 54.35; H: 4.56; N: 24.38; found: C: 54.50;
H: 4.65; N: 24.51.
Mp., 85–88 °C; 1H NMR (300 MHz, CDCl3): δ 7.25–7.27
(m, 1H, thiophen), 7.78 (d, J = 3.9 Hz, 1H, thiophen), 7.85
(s, 1H, CH), 7.87 (d, J = 5.1 Hz, 1H, thiophen) ppm; 13C
NMR (75 MHz, CDCl3): δ 112.9, 113.8, 129.0, 135.4, 136.9,
138.1, 151.0 ppm; Anal. Calcd. for C8H5N5S: C: 47.28; H:
2.48; N: 34.46; S: 15.78; found: C: 47.44; H: 2.60; N: 34.62;
S: 15.94.
(E)‑3‑(2,4‑Dichlorophenyl)‑2‑(1H‑tetrazole‑5‑yl) acry‑
(E)‑3‑(2‑Pyridinyl)‑2‑(1H‑tetrazole‑5‑yl) acrylonitrile
lonitrile (4i)
(4o)
M.p., 142–143 °C; 1H NMR (300 MHz, CDCl3): δ 7.41 (dd,
J = 9.3, 1.8 Hz, 1H, Ar), 7.55 (d, J = 1.8 Hz, 1H, Ar);
8.11 (d, J = 8.4 Hz, 1H, Ar); 8.16 (s, 1H, CH) ppm; 13C
NMR (75 MHz, CDCl3): δ 86.0, 111.7, 113.0, 127.5, 128.3,
130.1, 130.7, 137.1, 141.0, 154.6 ppm; Anal. Calcd. for
M.p., 185–186 °C; 1H NMR (300 MHz, CDCl3): δ 7.79 (t,
J = 6.9 Hz, 1H, pyridine), 8.21 (d, J = 7.8 Hz, 1H, pyri-
dine), 8.59 (d, J = 7.2 Hz, 1H, pyridine), 8.72 (d, J = 4.5 Hz,
1H, pyridine) 9.39 (s, 1H, CH) ppm; 13C NMR (75 MHz,
CDCl3): δ 114.1, 116.1 122.2, 124.9, 129.9, 133.5, 136.4,
1 3

J IRAN CHEM SOC
20. S. Ozeki, J. Miyamoto, S. Ono, C. Wakai, T. Watanabe, J. Phys.
Chem. 100, 4205 (1996)
154.8 ppm; Anal. Calcd. for C9H6N6: C: 54.54; H: 3.05; N:
42.41; found: C: 54.70; H: 3.19; N: 42.28.
21. K.T. Chang, C.-I. Weng, J. Appl. Phys. 100, 043917 (2006)
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Acknowledgement We gratefully acknowledge the fnancial support
of the Research Council of the Shahrood University of Technology.
23. E. Chibowski, L. Hołysz, A. Szcześ, M. Chibowski, Colloid Surf.
A 225, 63 (2003)
24. J. Li, S. Luo, W. Yao, Z. Tang, Z. Zhang, M. Alim, J. Eur. Ceram.
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