Synthesis of 5-substituted 1H-tetrazoles using a recyclable heterogeneous nanonickel ferrite catalyst

Article abstract of DOI:10.1002/aoc.3358

An efficient method was developed for the [2 + 3] cycloaddition of sodium azide with nitriles to afford 5-substituted 1H-tetrazoles using nanonickel ferrite (NiFe₂O₄) as an effective heterogeneous catalyst in dimethylformamide. The main advantages of this method are high yields, simple methodology and easy work-up. The catalyst can be recovered and reused for several cycles with predictable activity.

Full text of DOI:10.1002/aoc.3358

Full paper
Received: 17 May 2015
Revised: 2 July 2015
Accepted: 8 July 2015
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/aoc.3358
Synthesis of 5-substituted 1H-tetrazoles using a
recyclable heterogeneous nanonickel
ferrite catalyst
Fatemeh Abrishamia*, Maryam Ebrahimikiaa and Fatemeh Rafieeb
An efficient method was developed for the [2 + 3] cycloaddition of sodium azide with nitriles to afford 5-substituted 1H-tetrazoles
using nanonickel ferrite (NiFe2O4) as an effective heterogeneous catalyst in dimethylformamide. The main advantages of this
method are high yields, simple methodology and easy work-up. The catalyst can be recovered and reused for several cycles with
predictable activity. Copyright © 2015 John Wiley & Sons, Ltd.
Keywords: heterogeneous catalyst; nickel ferrite nanoparticles; cycloaddition; 5-substituted 1H-tetrazoles
nano-ZnO/Co2O3,[31] CoY zeolite,[7] CuFe2O4 nanoparticles,[32] zeo-lite/
Introduction
sulfated zirconia,[33] phosphomolybdic acid,[34] amberlyst-15[35] and
Ln(OTf)3-SiO2.[36]
Tetrazoles are synthetic nitrogen-rich compounds with a wide
range of applications that are receiving considerable attention
Herein, we report the synthesis of 5-substituted 1H-tetrazoles
among the stable heterocycles.[1] They play important roles in coor-
from various aryl/heteroaryl cyanides and sodium azide under
dination chemistry,[2] in the photographic industry[3] and in the for-
conventional heating using nickel ferrite (NiFe2O4) nanoparticles
mation of photoinducible bioorthogonal ligations for the selective
as a recyclable catalyst. Nickel ferrite nanoparticles are one of the
covalent attachment of synthetic groups to biopolymers such as
most important members of the spinel ferrites, a main category of
proteins.[4] Furthermore, extensive work has been accomplished
bimetallic nanoparticles displaying very good catalytic activity in
in the field of medicinal chemistry.[5] They are used for their biolog-
various organic reactions. Use of bimetallic nanoparticles as a
ical activities such as antibacterial, anti-inflammatory, antifungal,
catalyst leads to better selectivity and catalytic activity and higher
antiviral, antituberculous, cyclo-oxygenase inhibitory, antinociceptive,
deactivation resistance compared to monometallic ones.
hypoglycaemic and anticancer activities.[6] Tetrazole moieties
are also important synthons in synthetic organic chemistry. For
example, a proline-derived tetrazole is used as an enantioselective
catalyst in asymmetric synthesis and multicomponent reactions.[7] Results and discussion
As a result of their acidities, 5-monosubstituted tetrazoles are also
used as activators in oligonucleotide synthesis.[8]
Conventional synthesis of 5-substituted 1H-tetrazoles is via [2 + 3]
Nickel ferrite nanoparticles were prepared using a co-precipitation
method according to the procedure presented by Aliahmad and
Noori.[37] In the first step of the process, Ni(OH)2 and Fe(OH)3 are ob-
cycloaddition of azides to the corresponding nitriles, first reported by
Hantzsch and Vagt.[9] Various synthetic approaches have been
tained with a higher reaction activity. When the solution is heated
to 70°C, the metal hydroxides are decomposed to produce NiO
developed for this transformation. Most of them depend on the in
situ production of highly toxic, explosive, water-sensitive and volatile
hydrazoic acid through activation of the azide by expensive and toxic
and Fe2O3 in the reaction process (Scheme 1). Nickel ferrite nano-
particles are formed when the sample is calcined at 500°C for 3h.[38]
In order to characterize the catalyst structure, the synthesized
metal organic azide complexes such as those of tin or silicon, strong
Lewis acids or amine salts.[10] Later, a dramatic procedure involving
nanoparticles were analysed using Fourier transform infrared (FT-IR)
spectroscopy, X-ray fluorescence (XRF), X-ray diffraction (XRD) and
stoichiometric amounts of Zn(II) salts was reported under reflux in
H2O.[11] Other recent developments include the synthesis of 5-
scanning electron microscopy (SEM).
substituted 1H-tetrazoles under solvent-free conditions,[12] and the
use of various catalysts such as Cu2O,[13] BF3ꢀOEt2,[14] Pd(OAc)2/
ZnBr2,[11] Yb(OTf)3,[15] Zn(OTf)3,[16] AlCl3,[17] CuSO4,[18] Pd(PPh3)4,[19]
*
Correspondence to: Fatemeh Abrishami, Department of Chemistry, Faculty of
Chemistry and Chemical Engineering, Malek-ashtar University of Technology,
Tehran, Iran. E-mail: fatemeabrishami@yahoo.com
TMSN3/TABF[12] and boron azides.[20] However, a drawback of
these homogeneous catalytic processes is the difficulty in separation
and recovery of the catalysts. Therefore, many researchers have
developed various heterogeneous catalyst systems, such as
silica-supported FeCl3,[21] ZnS nanospheres,[22] Cu–Zn alloy nano-
powder,[23] Zn/Al hydrotalcite,[24] Sb2O3,[25] zinc hydroxyapatite,[26]
CdCl2,[27] metal tungstates,[28] γ-Fe2O3,[29] natural natrolite zeolite,[30]
a Department of Chemistry, Faculty of Chemistry and Chemical Engineering,
Malek-ashtar University of Technology, Tehran, Iran
b
Department of Chemistry, Faculty of Physics-Chemistry, Alzahra University, Vanak,
Tehran, Iran
Appl. Organometal. Chem. (2015)
Copyright © 2015 John Wiley & Sons, Ltd.

F. Abrishami et al.
Scheme 1. Synthesis of nickel ferrite nanoparticles.
The FT-IR spectrum of nickel ferrite nanoparticles (Fig. 1) shows
broad bands at 3438 and 1632 cmꢁ1 assigned to OH stretching
and bending modes of water, respectively. Intrinsic stretching
vibration of the metal atom at the tetrahedral site, Mtetra↔O (ν1),
is observed at 573 cmꢁ1, and the characteristic band at 401 cmꢁ1
(ν2) is attributed to octahedrally bonded metal atom stretching
vibrations, Mocta↔O. The different frequencies of the characteristic
vibrations (ν1 and ν2) may be attributed to the long bond length of
oxygen–metals ions in the octahedral sites (Fe–O) and shorter bond
length of oxygen–metals ions in the tetrahedral sites (Ni–O).[39]
The XRF results indicate that the amount of elemental Ni is
23.47%. This is in very good accordance with the formulation of
the nickel ferrite structure, NiFe2O4.
Figure 2. XRD pattern of nickel ferrite nanoparticles.
The powder XRD pattern of the nickel ferrite nanoparticles is
shown in Fig. 2. The diffraction peaks observed at 2θ = 30.70°,
36.02°, 37.6°, 43.92°, 54.28°, 57.77° and 63.4° correspond to the
planes of (220), (311), (222), (400), (422), (511) and (440), respec-
tively. The (311) peak has the highest intensity in the XRD pattern.
All of the Bragg reflection peaks confirm the formation of NiFe2O4.
No diffraction peaks of impurities such as α-Fe2O3 or NiO and other
secondary phases are detected. It is clearly observed that the
reflection peaks are sharp and narrow, indicating a high degree of
crystallinity and phase purity of the product. The diffraction lines
provide clear evidence for the formation of the cubic spinel
structure of nickel ferrite with lattice parameter α = 8.34 Å.
The surface morphology, orientation and particle sizes of the
nickel ferrite nanoparticles were determined using SEM. The SEM
images (Fig. 3) show a relatively uniform dispersion of nanoparticles
with an average particle size of ca 10 nm.
After confirming the exact characteristics of the catalyst, the
catalytic activity of the nanoparticles was examined in the synthesis
of 5-substituted 1H-tetrazoles from various aryl/heteroaryl cya-
nides. In order to improve the efficiency of the reaction, the solvent
was optimized at different temperatures and in the presence of
various concentrations of catalyst. Initially, the reaction conditions
were optimized for the reaction of 4-chlorobenzonitrile with
sodium azide in the presence of various solvents using 5 mol% of
catalyst (Table 1). Several organic solvents, namely tetrahydrofuran
(THF), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF),
dioxane and toluene, and also water as a green and non-toxic
solvent were examined. According to the data in Table 1, DMF is
the most efficient solvent for this reaction (Table 1, entry 9).
To study the effects of temperature, the reaction was initially car-
ried out at room temperature and then at each of 50, 80, 100 and
120°C (Table 1, entries 6–10). It is evident from Table 1 that the yield
of the reaction is considerably enhanced at 100°C. The yield
remains almost constant at higher temperature.
Determination of the amount of catalyst required for the reaction
is the next step. For this purpose, the reaction was carried out in the
absence of the catalyst and also in the presence of 2, 5 and 10 mol%
of the nanonickel ferrite catalyst under the obtained optimized
reaction conditions: 5 mol% gives the best results (Table 1, entries
9 and 11–13). The reaction was evaluated in the absence of ammo-
nium acetate. A longer time is required for the reaction to complete
under this condition (Table 1, entry 14).
With these optimized reaction conditions in hand, the generality
of this catalytic system for the synthesis of 5-substituted 1H-
tetrazoles from various aryl/heteroaryl cyanides was explored. As
evident from Table 2, reactions of m- and p-cyanopyridine with
sodium azide afford nearly stoichiometric amounts of the products
(Table 2, entries 3 and 4). The activity of nitrile compound towards
azide ion plays an important role in this cycloaddition reaction.
Among the various nitrile compounds, aromatic nitriles with
electron-withdrawing substituents give higher yields in shorter
reaction times (Table 2, entries 5, 8 and 12). However, when a nitrile
bearing an electron-donating group is used as the reactant (Table 2,
entries 6 and 7), the corresponding tetrazole is obtained in mode-
rate to good yields with a prolonged reaction time. Malononitrile
affords only mono-addition product even on addition of 2 equiv.
of sodium azide (Table 2, entry 9).
1,4-Dicyanobenzene is an interesting substrate for study of
mono-addition or di-addition reactions. It has been reported that
the di-addition product is obtained using soluble Zn(II) salts as
catalyst, whereas the mono-addition product is obtained with the
use of solid zinc oxide catalyst. He and co-workers found that
mono- and di-addition products could be selectively synthesized
by simply adjusting the molar ratio of NaN3 to nitriles and the rate
of addition of NaN3 to the reaction solution.[28] The di-addition
Figure 1. FT-IR spectrum of NiFe2O4 nanoparticles synthesized using a co-
precipitation method.
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Copyright © 2015 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. (2015)

Synthesis of 5-substituted 1H-tetrazoles catalysed by NiFe2O4
Table 1. Optimization of reaction conditions for the synthesis of 5-(4-
chlorophenyl)-1H-tetrazole under conventional heating conditionsa
Entry
Solvent
Catalyst
(mol%)
Temperature
(°C)
Time
(h)
Yield
(%)b
1
THF
5
5
Reflux
120
2
2
10
94
8
2
DMSO
Dioxane
Toluene
H2O
3
5
Reflux
Reflux
Reflux
Room temp.
50
2
4
5
2
20
30
60
75
80
98
98
0
5
5
7
6
DMF
5
2
7
DMF
5
2
8
DMF
5
80
2
9
DMF
5
100
2
10
11
12
13
14c
DMF
5
120
2
DMF
—
2
100
4
DMF
100
2
44
98
96
DMF
10
5
100
2
DMF
100
11
aReactions conditions: 4-chlorobenzonitrile (1 mmol), NaN3 (1.3 mmol),
NH4OAc (1 mmol), solvent (3 ml).
bYield of isolated product.
cIn the absence of ammonium acetate.
with sodium azide, the catalyst was separated from the reaction
mixture with an external magnet, washed three times with 5 ml
of acetone and then with doubly distilled water several times,
and dried in an oven at 100°C for 3–4 h. This process assists in
Table 2. Synthesis of 5-substituted 1H-tetrazoles catalysed by nickel
ferrite nanoparticles (Ni-Ferrite NPs)a
Entry
R
Time (h) Yield (%)b
M.p. (°C)c
Figure 3. SEM images of synthesized nickel ferrite nanoparticles.
1
C6H5-
3
94
98
95
96
95
90
80
98
96
97
94
95
215–217 (215–216)[7]
260–261 (261–263)[7]
225–226 (224–225)[4]
250–252 (251–253)[4]
209–211 (210)[40]
247–249 (248–250)[40]
142–145 (143–144)[41]
257–258 (258–260)[33]
115–117 (116–118)[7]
123–125 (123–124)[7]
146–147 (145–148)[7]
214–216 (215–217)[4]
2
p-ClC6H4-
3-Pyridinyl-
4-Pyridinyl-
p-FC6H4-
2
3
3
product was obtained when the molar ratio of NaN3 to nitrile was
about 2; whereas when the molar ratio was about 1, the methodol-
ogy of adding NaN3 to the reaction solution had a crucial influence
on the formation of mono- and di-addition products. If NaN3 is
completely added into the reaction solution before the chemical
reaction, both adducts are formed with similar yields (61:24). This
indicates that the substrate and mono-addition products show
similar reaction activity with NaN3. On the other hand, if NaN3 is
added gradually over a period of 6 h, the dominant product is the
mono-addition one.[29] It is noteworthy that 1,4-dicyanobenzene
only gives mono-adduct even when using a 1:2 molar ratio of
1,4-dicyanobenzene to sodium azide and 10 mol% of NiFe2O4
(Table 2, entry 8).
4
2
5
1
6
p-CH3C6H4-
o-NH2C6H4-
p-CNC6H4-
CNCH2-
3
7
3
8
2
9d
10
11e
12
1.5
1
C6H5CH2-
CH3
1
p-NO2C6H4-
1
aReaction conditions: nitrile (1 mmol), sodium azide (1.3 mmol),
ammonium acetate (1 mmol), catalyst (5 mol%), DMF (3 ml) at 100°C.
bYield of isolated product.
cLiterature values in parentheses.
dReaction carried out in a pressure tube with 1.3 and 2.6 mmol of
NaN3.
The importance of a heterogeneous catalyst over its homoge-
neous counterpart is the ease of separation and reusability with-
out loss of activity. The recovery and reusability of the catalyst
were investigated in tetrazole formation under the optimized
conditions. After completion of the reaction of 4-chloroben-zonitrile
eReaction carried out in a pressure tube.
Appl. Organometal. Chem. (2015)
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F. Abrishami et al.
keeping the catalyst surface active. Then the recovered catalyst
was used in the next run. It is noteworthy that the recycled
catalyst retains optimum activity until the fourth cycle after which
a drop in yield is observed (Fig. 4).
Table 3. Comparison of various heterogeneous catalysts in 5-phenyl-
1H-tetrazole formation
Entry
Catalyst
Temperature Time Yield
Ref.
(°C)
(h)
(%)
To evaluate the leaching phenomenon of the catalyst as a het-
erogeneous catalytic system, the reaction of 4-chlorobenzonitrile
with sodium azide was repeated under optimized conditions in
a defined time (1 h). However, for this bimetallic compound there
is no support and the whole catalyst is a single spinel structure
and therefore no leaching effect is observed in a formal form.[42]
As evident from Table 2, this reaction completes in 2 h and it
gives only 60% yield after 1 h. Then the catalyst nanoparticles
were collected from the reaction mixture with an external magnet
and the reaction was continued under the same conditions. After
another 1 h, the reaction was stopped and its completion was
again examined. The results show that the reaction in the absence
of the catalyst no longer proceeds. This observation confirms that
no leaching occurs in the reaction medium during the course of
the reaction.
1
CoY zeolite
120
120
120
120
120
120
120
100
120
120
120
14
12
12
14
12
24
12
3
90
84
79
72
78
72
82
7
24
21
43
26
29
32
2
Zn/Al hydrotalcite
FeCl3–SiO2
3
4
Nano-ZnO
5
Zinc hydroxyapatite
CuWO4ꢀ2H2O
CuFe2O4
6
7
8
Nanonickel ferrite
γ-Fe2O3
Sulfated zirconia
Mesoporous ZnS
nanospheres
94 This work
9
36
24
36
81
90
96
30
33
22
10
11
The efficiency of the catalyst was determined by comparison
with other heterogeneous catalytic systems. It gives a better yield
in shorter time (Table 3).
A plausible reaction pathway is proposed for the synthesis of
5-substituted 1H-tetrazoles using nickel ferrite nanoparticles as
catalyst, as shown in Scheme 2. Initially, coordination of nitrogen
atoms of nitrile and azide compounds with Ni(II) forms complex
I which accelerates the cyclization step. This idea is supported
by performing the reaction in the absence of NiFe2O4. Without
any catalyst, cycloaddition reaction is not completed even after
a long period of time (Table 1, entry 11). The [3 + 2] cycloaddition
between the C≡N bond of nitrile compound and azide ion takes
place readily to form the intermediate II. Protonolysis of interme-
diate II by H+ of NH4OAc or acidic extraction with HCl affords
the 5-substituted 1H-tetrazole and NiFe2O4 catalyst. Ammonium
acetate may produce ammonium azide in situ by reaction of
ammonium acetate and sodium azide, increasing the availability
of azide ion for [3 + 2] cycloaddition with nitrile, and also ammonium
acetate is used as proton source to provide pure tetrazoles.[44,45]
Scheme 2. Plausible mechanism for the formation of tetrazoles.
1
obtained with Nicolet 800 spectrophotometer using KBr discs. H
NMR and 13C NMR spectra were recorded with a Bruker (Avance
DRX-500) spectrometer at 500 and 125 MHz, respectively; using
DMSO-d6 as solvent at room temperature. Chemical shifts were re-
ported in ppm relative to tetramethylsilane as an internal standard.
XRD patterns of the catalyst were recorded with a PW 3710 X-ray
diffractometer (Philips) at room temperature using monochromatic
Cu Kα radiation with a wavelength of λ = 0.15418 nm. The peak
position and intensity were obtained between 20° and 70° with a
rate of 0.04° sꢁ1. The morphology of the catalyst was observed
using a TSCAN SEM instrument.
Experimental
General
All melting points were determined in open capillaries with a
Gallenkamp instrument. The FT-IR adsorption spectra were
All reagents and solvents used in this study were commer-
cially available and were purchased from commercial suppliers
(Acros, Merck and Aldrich) and used without any additional
purification.
Synthesis of nickel ferrite (NiFe2O4)
Solutions of iron chloride (FeCl3ꢀ6H2O) (0.2 M) and nickel chloride
(NiCl2ꢀ6H2O) (0.1 M) were prepared separately and mixed together.
In order for the pH to reach 13, a solution of NaOH (3 M) was
added slowly to the flask. Finally, oleic acid (3 drops) was added
to the solution as a surfactant and the suspension was vigorously
stirred using a magnetic stirring bar at 70°C for 2 h. After complete
precipitation, the residue was washed with double-distilled water
(3 × 25 ml) and dried in an oven at 90°C overnight. It was then
calcined at 500°C for 3 h.
Figure 4. Recovery and reuse of nickel ferrite nanoparticles for the
synthesis of 5-(4-chlorophenyl)-1H-tetrazole.
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Appl. Organometal. Chem. (2015)

Synthesis of 5-substituted 1H-tetrazoles catalysed by NiFe2O4
General procedure for preparation of 5-substituted 1H-
Acknowledgment
tetrazole
We gratefully acknowledge the funding support received for this
project from Malek-ashtar University of Technology (MUT), Islamic
Republic of Iran.
In a round-bottom flask equipped with a condenser for refluxing
and a magnetic stirring bar, aryl/heteroaryl cyanide (1 mmol),
sodium azide (1.3 mmol), ammonium acetate (1 mmol), nickel
ferrite nanoparticles (5 mol%) and DMF (3 mL) were added
and heated at 100°C under air atmosphere. The mixture was
vigorously stirred under these reaction conditions and reaction
completion was monitored using TLC (EtOAc–n-hexane, 75:25).
After completion of the reaction, the catalyst was separated
from the reaction mixture with an external magnet and the
reaction mixture was treated with ethyl acetate (10 ml). The
organic layer was treated with HCl (10 ml, 5 N) and stirred
vigorously. The resultant organic layer was separated, and the
aqueous layer was again extracted with ethyl acetate (10 ml).
The combined organic layers were washed with water, dried
over anhydrous magnesium sulfate and concentrated under
reduced pressure using a rotary evaporator to give the crude solid
crystalline 5-substituted 1H-tetrazole. The crude solid product was
purified using silica gel column chromatography (EtOAc–n-hexane,
75:25).
References
[1] R. N. Butler, in Comprehensive Heterocyclic Chemistry II, Vol. 4 (Eds.: A. R.
Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, Oxford, 1996.
[2] P. N. Gaponik, S. V. Voitekhovich, O. A. Ivashkevich, Russ. J. Chem. Rev.
2006, 75, 507.
[3] R. C. Tuites, T. E. Whiteley, L. M. Minsk, US Patent 1,245,614, 1971.
[4] A. Xie, M. Cao, Y. Liu, L. Feng, X. Hu, W. Dong, Eur. J. Org. Chem. 2014,
436.
[5] a) E. Makino, N. Iwasaki, N. Yagi, H. Kato, Y. Ito, H. Azuma, Chem. Pharm.
Bull. 1990, 38, 201; b) S. J. Wittenberger, Org. Prep. Proced. Int. 1994, 26,
499; c) M. Uchida, M. Komatsu, S. Morita, T. Kanbe, K. Nagakawa, Chem.
Pharm. Bull. 1989, 37, 322; d) S. Wu, A. Fluxe, J. Sheffer, J. M. Janusz,
B. E. Blass, R. White, C. Jackson, R. Hedges, M. Muawsky, B. Fang,
G. M. Fadayel, M. Hare, L. Djandjighian, Bioorg. Med. Chem. Lett. 2006,
16, 6213; e) C. T. Alabaster, A. S. Bell, S. F. Campbell, P. Ellis,
C. G. Henderson, D. S. Morris, D. A. Roberts, K. S. Ruddock,
G. M. R. Samuels, M. H. Stefaniak, J. Med. Chem. 1989, 32, 575; f)
C. Liljebris, S. D. Larsen, D. Ogg, B. J. Palazuk, J. E. Bleasdale, J. Med.
Chem. 2002, 45, 1785; g) K. J. Wirth, T. Paehler, B. Rosenstein,
K. Knobloch, T. Maier, J. Frenzel, J. Brendel, A. E. Busch, M. Bleich,
Cardiovasc. Res. 2003, 60, 298; h) F. Ahmad, J. L. Azevedo, R. Cortright,
G. L. Dohm, B. J. Goldstein, J. Clin. Invest. 1997, 100, 449.
[6] P. B. Mohite, V. H. Bhaskar, Int. J. PharmTech Res. 2011, 3, 1557.
[7] V. Rama, K. Kanagaraj, K. Pitchumani, J. Org. Chem. 2011, 76, 9090.
[8] R. Welz, S. Muller, Tetrahedron Lett. 2002, 43, 795.
All synthesized tetrazoles were characterized using spectral
data (FT-IR, H NMR and 13C NMR) and melting points and com-
1
paring them with authentic samples.[4,7,33,40] The FT-IR spectra of
synthesized compounds showed a sharp absorption at 3421
cmꢁ1 (N–H), a group of bands at 1455 (C–H), 1285 (N–N¼N–),
1208, 1120 and 1048 cmꢁ1 caused by the presence of secondary
amino group and tetrazole ring, and the absence of a band at
2200 cmꢁ1 of the CN group. For example, the spectroscopic data
for some products are presented in the following.
[9] A. Hantzsch, A. Vagt, Justus Liebig’s Ann. Chem. 1901, 314, 339.
[10] O. G. Mancheño, C. Bolm, Org. Lett. 2007, 9, 2951.
[11] Y. Zhu, Y. Ren, C. Cai, Helv. Chim. Acta 2009, 92, 171.
[12] D. Amantini, R. Beleggia, F. Fringuelli, F. Pizzo, L. Vaccoro, J. Org. Chem.
2004, 69, 2896.
5-Phenyl-1H-tetrazole (Table 2, entry 1). White solid; m.p.
1
215–216°C. H NMR (500 MHz, DMSO-d6, δ, ppm): 8.12–7.59 (m,
2H, Ph), 7.53–7.51 (m, 3H, Ph), 3.92 (br, 1H, N–H). 13C NMR (125
MHz, DMSO-d6, δ, ppm): 154.8 (tetrazole ring), 131.2 (Ph), 130.0
(Ph), 127.1 (Ph), 124.2 (Ph). FT-IR (KBr, cmꢁ1): 3426, 3130, 3055,
2980, 2915, 2840, 2688, 2598, 1608, 1565, 1486, 1409, 1255,
1164, 1056, 991, 790, 725.
[13] T. Jin, F. Kitahara, S. Kamjio, Y. Yamamoto, Tetrahedron Lett. 2008, 49,
2824.
[14] A. Kumar, R. Narayanan, H. Shechter, J. Org. Chem. 1996, 61, 4462.
[15] W. K. Su, Z. Hong, W. G. Shan, X. X. Zhang, Eur. J. Org. Chem. 2006, 2723.
[16] S. Hajra, D. Sinha, M. Bhowmick, J. Org. Chem. 2007, 72, 1852.
[17] D. P. Matthews, J. E. Green, A. J. Shuker, J. Comb. Chem. 2000, 2, 19.
[18] B. Akhlaghinia, S. Rezazadeh, J. Braz. Chem. Soc. 2012, 23, 2197.
[19] Y. S. Gyoung, J. G. Shim, Y. Yamamoto, Tetrahedron Lett. 2000, 41, 4193.
[20] Y. Yao, Y. Zhou, B. Lin, C. Yao, Tetrahedron Lett. 2013, 54, 6779.
[21] M. Nasrollahzadeh, Y. Bayat, D. Habibi, S. Moshaee, Tetrahedron Lett.
2009, 50, 4435.
[22] L. Lang, B. Li, W. Liu, L. Jiang, Z. Xu, G. Yin, Chem. Commun. 2010, 46,
448.
[23] G. Aridoss, K. K. Laali, Eur. J. Org. Chem. 2011, 6343.
[24] M. Lakshmi Kantam, K. B. Shiv Kumar, K. Phani Raja, J. Mol. Catal. A
2006, 247, 186.
[25] G. Venkateshwarlu, K. C. Rajanna, P. K. Saiprakash, Synth. Commun.
2009, 39, 426.
[26] M. Laxmi Kantam, V. Balasubramanyam, K. B. Shiva Kumar, Synth.
Commun. 2006, 36, 1809.
[27] G. Venkateshwarlu, A. Premalatha, K. C. Rajanna, P. K. Saiprakash, Synth.
Commun. 2009, 39, 4479.
[28] J. He, B. Li, F. Chen, Z. Xu, G. Yin, J. Mol. Catal. A 2009, 304, 135.
[29] G. Qi, Y. Dai, Chin. Chem. Lett. 2010, 21, 1029.
5-(4-Tolyl)tetrazole (Table 2, entry 6). White solid; m.p.
248–250°C. H NMR (500 MHz, DMSO-d6, δ, ppm): 7.93 (d, J = 9.0
1
Hz, 2H, Ph), 7.42 (d, J = 9.6 Hz, 2H, Ph), 3.35 (br, 1H, N–H), 2.4
(s, 3H, CH3). 13C NMR (125 MHz, DMSO-d6, δ, ppm): 155.0 (tetrazole
ring), 139.2 (Ph), 130.0 (Ph), 126.8 (Ph), 121.6 (Ph), 21.3 (CH3). FT-IR
(KBr, cmꢁ1): 3413, 3095, 3067, 2964, 2909, 2850, 1610, 1488, 1435,
1259, 1159, 1093, 1017, 871, 804.
4-(1H-Tetrazole-5-yl)benzonitrile (Table 2, entry 8). White solid;
m.p. 258–260°C. 1H NMR (500 MHz, DMSO-d6, δ, ppm): 8.21
(d, J = 9.9 Hz, 2H, Ph), 8.08 (d, J = 9.0 Hz, 2H, Ph). 13C NMR
(125 MHz, DMSO-d6, δ, ppm): 161.0 (tetrazole ring), 135.2 (Ph),
134.1 (Ph), 131.0 (Ph), 126.9 (CN), 115.3 (Ph). FT-IR (KBr, cmꢁ1):
3430, 3144, 3089, 3024, 2925, 2854, 2233, 1653, 1494, 1437, 1387,
1275, 1212, 1162, 1064, 995, 851, 746.
[30] M. Nasrollahzadeh, D. Habibi, Z. Shahkarami, Y. Bayat, Tetrahedron
2009, 65, 10715.
[31] S. M. Agawane, J. M. Nagarkar, Catal. Sci. Technol. 2012, 2, 1324.
[32] B. Sreedhar, A. Suresh Kumar, D. Yada, Tetrahedron Lett. 2011, 52, 3565.
[33] A. Teimouri, A. R. Najafi Chermahini, Polyhedron 2011, 30, 2606.
[34] S. Takale, S. Manave, K. Phatangare, V. Padalkar, N. Darvatkar,
A. Chaskar, Synth. Commun. 2012, 42, 2375.
[35] R. Shelkar, A. Singh, J. Nagarkar, Tetrahedron Lett. 2013, 54, 106.
[36] G. A. Meshram, S. S. Deshpande, P. A. Wagh, V. A. Vala, Tetrahedron Lett.
2014, 55, 3557.
Conclusions
We report that nanonickel ferrite is an effective heterogeneous
catalyst for the [2 + 3] cycloaddition of azide with a wide variety
of nitriles to form 5-substituted 1H-tetrazoles with good to excellent
yields. This catalyst can be separated and recovered easily from the
reaction solution and can be reused for at least five consecutive
runs without obvious loss in catalytic activity.
[37] M. Aliahmad, M. Noori, Indian J. Phys. 2013, 87, 431.
[38] A. Pui, D. Gherca, G. Carja, Dig. J. Nanomater. Biostruct. 2011, 6, 1783.
Appl. Organometal. Chem. (2015)
Copyright © 2015 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc

F. Abrishami et al.
[39] H. Kavas, N. Kasapoğlu, A. Baykal, Y. Köseoğlu, Chem. Pap. 2009, 63, 450.
[40] V. S. Patil, K. P. Nandre, A. U. Borse, S. V. Bhosale, E-J. Chem. 2012, 9,
1145.
[41] E. Wagner, J. Org. Chem. 1973, 38, 2976.
[42] F. Matloubi Moghaddam, G. Tavakoli, H. R. Rezvani, Appl. Organomet.
Chem. 2014, 28, 750.
[43] M. Lakshmi Kantam, K. B. Shiva Kumar, C. Sridhar, Adv. Synth. Catal.
2005, 347, 1212.
[44] D. R. Patil, M. B. Deshmukh, D. S. Dalal, J. Iran. Chem. Soc. 2012,
9, 799.
[45] H. Sharghi, S. Ebrahimpourmoghaddam, M. M. Doroodmand,
J. Organomet. Chem. 2013, 738, 41.
wileyonlinelibrary.com/journal/aoc
Copyright © 2015 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. (2015)