Synthesis of 5-substituted 1H-tetrazoles from aryl halides using nanopolymer-anchored palladium(II) complex as a new heterogeneous and reusable catalyst

Article abstract of DOI:10.1007/s00706-016-1732-8

Abstract: This paper reports on the preparation and use of chloromethylated polystyrene-anchored palladium(II) complex, [Ps-ttet-Pd(II)], as a separable nanocatalyst for the synthesis of 5-substituted 1H-tetrazoles by treating aryl halides with K₄[Fe(CN)₆] as non-toxic cyanide source, to generate in situ the corresponding aryl nitriles which then react through [2?+?3] cycloaddition with sodium azide. High yields of the products, simple methodology, easy work-up procedure, high catalytic activity, and superior cycling stability of the catalyst are the main advantages of this protocol. The structure of the catalyst was characterized using the powder XRD, SEM, TG-DTA, EDS, AAS, and FT-IR spectroscopy techniques. Graphical abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s00706-016-1732-8

Monatsh Chem
DOI 10.1007/s00706-016-1732-8
ORIGINAL PAPER
Synthesis of 5-substituted 1H-tetrazoles from aryl halides using
nanopolymer-anchored palladium(II) complex as a new
heterogeneous and reusable catalyst
1
1
2,3
1
Mahmood Tajbakhsh
•
Heshmatollah Alinezhad
•
Mahmoud Nasrollahzadeh
•
Taghi A. Kamali
Received: 22 January 2016 / Accepted: 7 March 2016
Ó Springer-Verlag Wien 2016
Abstract This paper reports on the preparation and use of
chloromethylated polystyrene-anchored palladium(II)
complex, [Ps-ttet-Pd(II)], as a separable nanocatalyst for
the synthesis of 5-substituted 1H-tetrazoles by treating aryl
halides with K [Fe(CN) ] as non-toxic cyanide source, to
Keywords 5-Substituted 1H-tetrazoles Á Aryl nitriles Á
Sodium azide Á Heterogeneous catalyst
Introduction
4
6
generate in situ the corresponding aryl nitriles which then
react through [2 ? 3] cycloaddition with sodium azide.
High yields of the products, simple methodology, easy
work-up procedure, high catalytic activity, and superior
cycling stability of the catalyst are the main advantages of
this protocol. The structure of the catalyst was character-
ized using the powder XRD, SEM, TG-DTA, EDS, AAS,
and FT-IR spectroscopy techniques.
The substituted benzonitriles represent important materi-
als for the preparation of different commercial
compounds, pharmaceutical, herbicides, pesticides, natural
products, dyes, and pigments [1–4]. Aryl nitriles valuable
intermediates in organic synthesis and can be easily
converted to a range of heterocycles, benzoic acids/esters,
amidines, amides, imidoesters, benzamidines, amines, and
aldehydes [5].
Graphical abstract
Tetrazoles are one of the important nitrogen-rich com-
pounds with a wide range of applications in the fields of
organic synthesis, pharmaceutical, coordination chemistry,
material science, especially explosives and in the synthesis
of N-containing heterocycles [6–10].
Classical methods for the preparation of benzonitriles
involve the Rosenmund-von Braun reaction of aryl halides
with stoichiometric amounts of copper(I) cyanide [11],
diazotization of anilines and subsequent Sandmeyer reac-
tion [12], and on an industrial scale the ammoxidation
reaction [13]. Modifications to these methods have been
made using palladium-, copper-, or nickel-catalyzed aryl
cyanation approaches [14, 15]. The transition metal-cat-
alyzed cyanation of aryl halides was performed using toxic
inorganic or organic cyanide sources such as alkali metal
cyanides (KCN [16], NaCN [17]), trimethylsilyl cyanide
(Me SiCN), [18] or Zn(CN) [19, 20]. The toxicity of KCN
&
Mahmoud Nasrollahzadeh
mahmoudnasr81@gmail.com
Heshmatollah Alinezhad
heshmat@umz.ac.ir
1
2
3
Faculty of Chemistry, University of Mazandaran, Babolsar,
Iran
3
2
and NaCN, the sensitivity of Me SiCN to moisture, the
3
Department of Chemistry, Faculty of Science, University of
Qom, P. O. Box 37185-359, Qom, Iran
release of HCN and production of heavy metal waste, in
the case of Zn(CN) , significantly restrict the applications
2
Center of Environmental Researches, University of Qom,
Qom, Iran
of these reagents. These difficulties have been overcome
123

M. Tajbakhsh et al.
using inexpensive and non-toxic potassium hexacyanofer-
rate(II), K [Fe(CN) ], as an efficient source of cyanide [21,
Catalyst was readily prepared in two steps. The syn-
thesis of the polymer-anchored Pd(II) complex is shown in
Scheme 2. Treatment of chloromethylated polystyrene
with phenylthiotetrazole in DMF, followed by the treat-
ment of the resulting phenylthiotetrazole-functionalized
polymer (1) with a solution of palladium(II) chloride in
ethanol resulted in covalent attachment of the palladium
complex to give the polymer-anchored Pd(II) complex
catalyst [Ps-ttet-Pd(II)] (2).
4
6
2
2].
On the other hand, the most conventional methods for
the synthesis of 5-substituted 1H-tetrazoles is via [2 ? 3]
cycloaddition between corresponding nitriles and azides.
Several methods for the synthesis of 5-substituted tetra-
zoles have been reported through the cycloaddition of
nitriles using NaN or TMSN in the presence of homo-
3
3
geneous and heterogeneous catalysts such as Zn(II) [23],
AlCl [24], BF -OEt [25], FeCl –SiO [26], Zn/Al HT
3
3
2
3
2
[
27], ZnS [28], Pd(PPh ) [29], and GO/ZnO nanocom-
3
Results and discussion
4
posite [30].
However, despite these advances, papers reporting the
synthesis of 5-substituted 1H-tetrazoles from in situ formed
benzonitriles have stayed sparse. The successful examples
for the one-pot synthesis of 5-substituted 1H-tetrazoles are
based on the direct transformation of primary alcohols and
aldehydes into tetrazoles in aqueous media [31, 32], and
the sequential one-pot synthesis of tetrazoles from aryl
halides using toxic cyanide sources [33–36]. Despite the
advantages of homogeneous catalysts, difficulties in
recovering the catalyst from the reaction mixture severely
inhibit their wide use in industry.
Successful synthesis of the [Ps-ttet-Pd(II)] was character-
ized using powder XRD, SEM, TG-DTA, EDS, AAS and
FT-IR. The presence of the phenyl-1H-tetrazole-5-thiol
ligand bonded CMP and the formation of [PS-ttet-Pd(II)]
(2) were verified by FT-IR. The FT-IR spectrum of the
chloromethylated polystyrene was compared with the
thiotetrazole bonded polystyrene (1) and nanopolymer-an-
chored [PS-ttet-Pd(II)] (2) catalyst to confirm the
coordination of the metal atom with the phenyl-1H-tetra-
zole-5-thiol ligand (Fig. 1). As depicted in Fig. 1a, the
-
1
sharp C–Cl peak (due to CH Cl groups) at 1274 cm in
2
Development of heterogeneous catalysts for industrial
applications has become important from both the envi-
ronmental and economic viewpoints, and has been
reviewed in the literature [37]. The use of heterogeneous
catalysts such as organometallic complexes onto a solid
support is often desirable from the perspective of process
development due to their recycling, simple recovery, and
easy handling [38]. The use of heterogeneous catalysts for
coupling reactions gives rise to a reduction in waste. As
such, highly active polymer-anchored transition metal
complexes have gained significant interest because they
could be easily recovered and reused [39]. We used
chloromethylated polystyrene (CMP) cross-linked with
the starting polymer practically decreased or was seen as a
weak band after introduction of the thiotetrazole ligand on
the polymer. The stretching vibrations of the N=N double
-
1
bonds appear at 1449 and 1403 cm for polystyrene-an-
chored ligand (Fig. 1a) and complex (Fig. 1b),
-
1
respectively. Signals ranging under 3000–2800 cm
identify the methylene stretching bonds. The functionalized
-
1
beads exhibited a band at 1652 cm due to stretching
vibrations of the C=N double bond, which was shifted to
-
1
1598 cm
in the anchored beads. This verified that a
metal complex was formed on the surface of the polymer.
The presence of polystyrene and palladium was con-
firmed with powder XRD measurements. The powder
X-ray diffraction pattern of the complex is shown in Fig. 2.
Polystyrene displays a broad peak at about 2h = 22.7°
[48]. The size of the [PS-ttet-Pd(II)] catalyst can be found
by applying Sherrer’s equation and the average size is
found to be 30 nm.
2
% of divinylbenzene (DVB) as a support because it is a
popular polymeric material due to its ready availability,
low cost, ease of functionalization, and mechanical
robustness.
In continuation of our recent works on the synthesis of
tetrazoles and applications of heterogeneous catalysts [40–
Scanning electron micrograph (SEM) was recorded to
understand the morphological changes occurring on the
surface of the polystyrene. Figure 3 shows SEM images of
the polymer-anchored complex in different magnifications.
As expected, the pure polystyrene bead had a smooth and
flat surface [49], while the supported complex showed
roughening of the top layer. On the other hand, after metal
loading on the surface of the polymer, a change in mor-
phology of the polymer surface is observed and the smooth
and flat surface of the polymer shows a slight roughening
on complexation.
4
7], we herein report a new protocol for the preparation
and characterization of the nanopolystyrene-anchored
Pd(II) thiotetrazole complex abbreviated as [Ps-ttet-Pd(II)]
(
2) and its application as a new and stable heterogeneous
catalyst for the cyanation of aryl halides to the corre-
sponding benzonitriles by the use of potassium
hexacyanoferrate(II), K [Fe(CN) ], as a non-toxic cyanide
4
6
source. The formed benzonitriles without isolation under-
went [2 ? 3] cycloaddition with sodium azide to afford
high yields of the desired tetrazoles (Scheme 1).
1
23

Synthesis of 5-substituted 1H-tetrazoles from aryl halides using nanopolymer-anchored…
Scheme 1
Scheme 2
Fig. 1 FT-IR spectra of
a thiotetrazole ligand bonded
polystyrene and b nanopolymer-
anchored [PS-ttet-Pd(II)]
complex
123

M. Tajbakhsh et al.
Fig. 2 XRD pattern of the [PS-
ttet-Pd(II)] complex
Fig. 3 SEM images of the [PS-ttet-Pd(II)] complex
We used energy dispersive X-ray spectroscopy (EDS) to
determine chemical composition of the catalyst. The
presence of the Pd is verified by EDS. In the EDS spectrum
of catalyst (Fig. 4), peaks related to C, S, Pd, Cl, and O
were observed. The excess oxygen is due to physical
absorption of oxygen from environment during sample
preparation for SEM experiment. The metal loading of
polymer-supported palladium complex, as determined by
atomic absorption spectrometry, was 0.29 mmol/g.
C K
3
0000
25000
2
1
1
0000
5000
0000
AuM
AuM PdL
PdL
ClK
S K
TGA curve of the chloromethylated polystyrene-an-
chored palladium(II) complex is shown in Fig. 5. Thermal
stability of polymer-anchored complex was measured using
S K
5
000
K K
ClK
O K
AuL 2
AuL
K K
AuLl
AuL
keV
0
-
1
0
5
10
TG-DTA at a heating rate of 2 °C min in air over a
temperature range of 30–600 °C. TGA of chloromethylated
Fig. 4 EDS spectrum of the [PS-ttet-Pd(II)] complex
1
23

Synthesis of 5-substituted 1H-tetrazoles from aryl halides using nanopolymer-anchored…
Fig. 5 Thermal studies of the
[
PS-ttet-Pd(II)] complex
polystyrene-anchored palladium(II) complex indicates that
thermolysis of the phenylthiotetrazole ligand bound to the
polymer proceeds at higher temperatures in comparison
with the free ligand molecule. Thus, whereas pure
phenylthiotetrazole decomposes at about 140 °C [50],
being deposited on the surface of complex, it decomposes
at about 220 °C. Also, we can see another degradation step,
roughly 280–470 °C, could be due to the degradation of the
polystyrene as reported in the literature [51].
hexacyanoferrate(II), and sodium azide in the presence of
the [PS-ttet-Pd(II)] (Table 1). The reaction conditions were
optimized and the best conditions were found to be 0.05 g of
catalyst, 0.22 mmol of K [Fe(CN) ] in N,N-dimethylform-
4
6
amide as solvent and the results are summarized in Table 1.
Several bases were screened for the reaction in the presence
of a catalytic amount of the [PS-ttet-Pd(II)] catalyst. As
shown in Table 1, the reaction was influenced significantly
by the base employed. The reaction worked very well when
inorganic bases such as Na CO and K CO were used
In next step, we tested the catalytic activity of the [PS-
ttet-Pd(II)] in tandem synthesis of 5-substituted 1H-tetra-
zoles from aryl halides with K [Fe(CN) ] as non-toxic
2
3
2
3
(entries 7 and 8), and the best result was obtained in the case
of Na CO (entry 7). Control experiments show that there is
4
6
2
3
cyanide source. Initial studies were performed to optimize
the reaction conditions between iodobenzene, potassium
no reaction in the absence of catalyst (Table 1, entry 9). A
decrease in the catalyst loading from 0.05 to 0.02 g afforded
Table 1 Optimization of the synthesis of 5-phenyl-1H-tetrazole
b
Entry
[PS-ttet-Pd(II)]/g
Solvent
Base
Temp./°C
Yield/%
1
2
3
4
5
6
7
8
9
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
–
DMF
DMF
Et
3
N
120
120
80
45
35
0
Piperidine
CH
3
CN
Na
Na
Na
Na
Na
2
CO
2
CO
2
CO
2
CO
2
CO
3
3
3
3
3
Toluene
NMP
110
120
120
120
120
120
120
120
Trace
50
65
89
81
0
DMAC
DMF
DMF
K
2
CO
3
DMF
Na
Na
Na
2
2
2
CO
3
3
3
1
1
a
0
1
0.02
0.08
DMF
CO
CO
70
90
DMF
Reaction conditions: iodobenzene (1 mmol), K
3
cm degassed DMF at 120 °C for 12 h
Isolated yield
4
[Fe(CN) ] (0.22 mmol), base (1 mmol), 0.05 g [Ps-ttet-Pd(II)], sodium azide (1.5 mmol),
6
5
b
123

M. Tajbakhsh et al.
the product in lower yield (Table 1, entry 10). No significant
improvement on the yield was observed using higher
amount of the catalyst (Table 1, entry 11).
catalyst under the operating conditions. To investigate the
palladium leaching in this reaction, the filtrate of the reaction
after completion was analyzed by AAS technique. The
amount of palladium leaching after the second recycle was
determined by AAS analysis to be only 0.04 %, and after five
repeated recycling was 0.24 %.
To explore the general applicability of the [PS-ttet-
Pd(II)] as a catalyst for the synthesis of 5-sustituted 1H-
tetrazoles, different aryl halides contain both electron-re-
leasing and electron-withdrawing groups were reacted with
K [Fe(CN) ] and NaN under optimal reaction conditions
In conclusion, we have proved that the heterogeneous
palladium catalyst [PS-ttet-Pd(II)] is a highly efficient and
stable catalyst for the synthesis of 5-substituted 1H-tetra-
zoles by treating aryl halides with K [Fe(CN) ], to generate
4
6
3
and the results are tabulated in Table 2. In all cases, the
electron-neutral, electron-rich and electron-poor aryl
halides give the corresponding products in good yields
under the standard reaction conditions. Aryl bromides, in
contrast to aryl iodides, require much longer periods of
time for the synthesis of 5-substituted 1H-tetrazoles.
The reusability of the catalyst is one of the most important
benefits and makes them useful for commercial applications.
The reusability of the catalyst was investigated for the syn-
thesis of 5-(4-methylphenyl)-1H-tetrazole under the present
reaction conditions (Table 2, entry 2). After completion of
the reaction, the [PS-ttet-Pd(II)] was separated from the
reaction mixture by centrifuge. The catalyst was washed with
water several times, dried, and employed for the next run.
The activity of the catalyst in five consecutive runs (85, 85,
4
6
in situ the corresponding aryl nitriles which then react
through [2 ? 3] cycloaddition with NaN . The catalyst was
3
characterized by FT-IR, SEM, EDS, XRD, AAS, and
TG-DTA analysis. This simple synthetic method has the
advantages of high yields, easy preparation, using non-toxic
potassium hexacyanoferrate(II) as cyanide source, elimina-
tion of dangerous and harmful hydrazoic acid, provides
simple work-up procedure, and handling of the catalyst. The
[PS-ttet-Pd(II)] is an eco-friendly catalyst because it can be
recovered and reused without any significant loss of activity.
Experimental All reagents were purchased from the
Merck and Aldrich chemical companies and used without
further purification. Chloromethylated polystyrene (4–5 %
Cl and 2 % cross-linked with divinylbenzene) was
8
3, 83, and 82 %) revealed the practical recyclability of the
catalyst. This reusability exhibits the high stability of the
Table 2 Sequential one-pot synthesis of 5-substituted 1H-tetrazoles from aryl halides with K
[Fe(CN) ] as non-toxic cyanide source
4 6
c
Entry
Aryl halide
Product
Time/h
Yield/%
89
M.p./°C (reported)
1
2
3
4
5
6
7
8
9
6
C H
5
I
C
6
H
5
Tet
4-MeC
4-MeOC
12
12
12
12
12
12
12
12
12
12
20
20
20
20
213–214 (215–216 [23])
248 (248–249 [34])
d
4-MeC
6 4
H I
6
H
4
Tet
85(82)
4-MeOC
6
5
H
4
I
6
5
4
H
4
Tet
83
86
86
81
80
84
81
78
81
77
79
75
232–233 (231–232 [34])
261–262 (262 [30])
4-ClC
6
H
H
I
4-ClC
6
H
H
Tet
Tet
3-ClC
6
4
I
3-ClC
6
137–139 (137–138 [52])
193 (193–194 [53])
6
4-FC H
4
I
6 4
4-FC H Tet
3-IC
4-IC
5
H
4
4
N
3-TetC
4-TetC
5
H
4
N
N
238-239 (239-240 [54])
254–255 (253–254 [54])
295 (290–291 [53])
5
H
N
5
H
4
1,4-I
2
C
6
H
4
4
1,4-(Tet)
1,3-(Tet)
2
C
6
H
H
4
4
1
1
1
1
1
a
0
1
2
3
4
1,3-I
2
C
6
H
2
C
6
258 (260 [55])
C
6
H
5
Br
4-MeC
3-ClC
3-BrC
C
6
H
5
Tet
4-MeC
3-ClC
3-TetC
213–214 (215–216 [23])
248 (248–249 [34])
6
H
4
Br
6
H
4
Tet
6
H
4
Br
6
H
4
Tet
137–139 (137–138 [52])
238–239 (239–240 [54])
5
H
4
N
5 4
H N
Reaction conditions: aryl halide (1 mmol), [K
3
4
Fe(CN)
6
2 3
] (0.22 mmol), Na CO (1 mmol), 0.05 g [Ps-ttet-Pd(II)], sodium azide (1.5 mmol),
5
cm degassed DMF at 120 °C
Products were identified by comparison of their melting point and H NMR spectral data those reported in the literature
b
1
c
Yield after work-up
Yield after fifth cycle
d
1
23

Synthesis of 5-substituted 1H-tetrazoles from aryl halides using nanopolymer-anchored…
purchased from Merck. Products were characterized by
1
different spectroscopic methods (FT-IR and H NMR
catalyst was centrifuged, washed with EtOH and the resi-
3
3
due was diluted with 35 cm ethyl acetate and 20 cm HCl
(4 N) and stirred vigorously. The resultant organic layer
was separated and the aqueous layer was extracted with
spectra) and melting points. The NMR spectra were
recorded on a Bruker Avance DRX 400 MHz instrument in
3
DMSO-d . The chemical shifts (d) are reported in ppm
25 cm ethyl acetate. The combined organic layer was
3
washed with 8 cm water and concentrated to give a crude
6
relative to the TMS as internal standard. J values are given
in Hz. FT-IR (KBr) spectra were recorded on a Perkin-
Elmer 781 spectrophotometer. Melting points were taken in
open capillary tubes with a BUCHI 510 melting point
apparatus and were uncorrected. TLC was performed on
silica gel polygram SIL G/UV 254 plates. X-ray diffraction
measurements were performed with a Philips powder
diffractometer type PW1373 goniometer. It was equipped
with a graphite monochromator crystal. The X-ray wave-
product. Column chromatography using silica gel gave the
1
pure product. All products were characterized by H NMR
and melting point which were in agreement with literature
[23, 30, 31, 35, 52–55].
Acknowledgments We gratefully acknowledge the Iranian Nano
Council and Universities of Mazandaran and Qom for the support of
this work.
´
˚
length was 1.5405 A and the diffraction patterns were
recorded in the range 2h = 0–90° with scanning speed of
°/min. Morphology and particle dispersion was investi-
References
2
gated by scanning electron microscopy (SEM) (Cam scan
MV2300). The chemical composition of the prepared
nanostructures was measured by EDS performed in SEM.
Palladium loadings were determined by atomic absorption
spectroscopy (AAS) using a VARIAN Spectra AA-20
instrument. Thermogravimetric-differential thermal analy-
1
2
3
. Weissman SA, Zewge D, Chen C (2005) J Org Chem 70:1508
. Zhang A, Neumeyer JL (2003) Org Lett 5:201
. Schareina T, Zapf A, Beller MJ (2004) Organomet Chem
689:4576
. Larock TRC (1989) Comprehensive organic transformations.
VCH, New York
4
5
. Rappoport Z (1970) Chemistry of the Cyano Group. Wiley,
London
6. Herr RJ (2002) J Bioorg Med Chem 10:3379
sis (TG-DTA) was performed using STA 1500 Rheometric
3
England). The flow rate of air was 120 cm /min and the
(
7
8
. Koldobskii GI, Ostrovskii VA (1994) Usp Khim 63:847
. Singh RP, Verma RD, Meshri DT, Shreeve JNM (2006) Angew
Chem Int Ed 45:3584
ramping rate of sample was 2 °C/min.
Preparation of nanopolystyrene-anchored Pd(II)
thiotetrazole complex
9
. Xue H, Gao Y, Twamley B, Shreeve JNM (2005) Chem Mater
17:191
0. Moderhack D (1998) J Prakt Chem 340:687
1
3
The reaction was performed in the 250 cm round-bot-
11. Copper LJ (1984) Tetrahedron 40:1433
1
2. Beletskaya IP, Sigeev AS, Peregudov AS, Petrovskii PV (2004) J
Organomet Chem 689:3810
tomed flask. To a mixture of 2.0 g CMP (1.25 mmol/g of
3
Cl) in 50 cm
DMF, 1-phenyl-1H-tetrazole-5-thiol
13. Hagedorn F, Gelbke HP (1979) In: Bartholome E, Biekert E,
Hellmann H, Ley H, Weigert WM, Weise E (eds) Ullmanns
Enzyklop a¨ die der technischen Chemie, 4th edn. Verlag Chemie,
Weinheim
(
5.0 mmol) and K CO3 (5.0 mmol) were added. The
2
mixture was stirred at 100 °C for 24 h, and then filtered,
washed with DMF, and finally dried under vacuum for
1
4. Wang D, Kuang L, Li Z, Ding K (2008) Synlett 69
1
2 h. The functionalized polymer (1) (1.0 g) was treated
15. Sundermeier M, Zapf A, Mutyala S, Baumann W, Sans J, Weiss
S, Beller M (2003) Chem Eur J 9:1828
3
with 0.45 g PdCl in 50 cm EtOH, and the mixture was
2
1
1
6. Liu Y, Shirakawa S, Maruoka K (2013) Org Lett 15:1230
7. Zanon J, Klapars A, Buchwald SL (2003) J Am Chem Soc
stirred under reflux conditions for 24 h. The resulting
polymer, impregnated with the metal complex, was filtered,
washed with EtOH, and subsequently dried at 60 °C to give
1
25:2890
18. Sundermeier M, Mutyala S, Zapf A, Spannenberg A, Beller
2003) J Organomet Chem 684:50
(
[
PS-ttet-Pd(II)] (Scheme 2).
1
9. Littke A, Soumeillant M, Kaltenbach RF, Cherney RJ, Tarby
CM, Kiau S (2007) Org Lett 9:1711
General procedure for the synthesis of 5-substituted
H-tetrazoles
2
0. Marcantonio KM, Frey LF, Liu Y, Chen Y, Strine J, Phenix B,
Chen CY (2004) Org Lett 6:3723
1
2
2
2
2
1. Schareina T, Zapf A, Beller M (2004) Chem Commun 1388–1389
2. Velmathi S, Leadbeater NE (2008) Tetrahedron Lett 49:4693
3. Demko ZP, Sharpless KB (2001) J Org Chem 66:7945
4. Habibi D, Nasrollahzadeh M, Bayat Y (2011) Synth Commun
41:2135
5. Kumar A, Narayanan R, Shechter H (1996) J Org Chem 61:4462
6. Nasrollahzadeh M, Bayat Y, Habibi D, Moshaee S (2009)
Tetrahedron Lett 50:4435
A mixture of aryl halide (1.0 mmol), K [Fe(CN) ]
4
6
(
(
0.22 mmol), 0.05 g [PS-ttet-Pd(II)], and sodium carbonate
3
1.0 mmol) was stirred in 5 cm DMF at 120 °C for 1 h
2
2
under an argon atmosphere. To the aryl nitrile compound
generated in situ was added sodium azide (1.5 mmol) and
the mixture was stirred at 120 °C for appropriate time.
After completion of the reaction (as indicated by TLC), the
2
7. Kantam ML, Kumar KS, Raja KP (2006) J Mol Catal A: Chem
247:186
123

M. Tajbakhsh et al.
2
2
8. Lang L, Li B, Liu W, Jiang L, Xu Z, Yin G (2010) Chem
Commun 46:448
9. Gyoung YS, Shim JG, Yamamoto Y (2000) Tetrahedron Lett
43. Nasrollahzadeh M, Sajadi SM (2016) J Colloid Interf Sci 462:243
44. Nasrollahzadeh M, Sajadi SM (2016) J Colloid Interf Sci 464:147
45. Nasrollahzadeh M, Sajadi SM (2015) Ceram Int 41:14435
46. Bakherad M, Keivanloo A, Bahramian B, Kamali TA (2009) J
Braz Chem Soc 20:907
47. Habibi D, Nasrollahzadeh M, Kamali TA (2011) Green Chem
13:3499
48. Chen Y, Zhao Y, Cai R, Huang ZE, Xiao L (1998) J Polym Sci
Part B Polym Phys 36:2653
4
1:4193
3
3
3
3
3
0. Nasrollahzadeh M, Jaleh B, Jabbari A (2014) RSC Adv 4:36713
1. Shie JJ, Fang JM (2003) J Org Chem 68:1158
2. Shie JJ, Fang JM (2007) J Org Chem 72:3141
3. Alterman M, Hallberg A (2000) J Org Chem 65:7984
4. Tao ZF, Li G, Tong Y, Stewart KD, Chen Z, Bui MH, Lin NH
(
2007) Bioorg Med Chem Lett 17:5944
49. Islam SM, Mondal S, Mondal P, Roy AS, Tuhina K, Salam N,
Mobarak M (2012) J Organomet Chem 696:4264
50. Nichick MN, Voitekhovich SV, Lesnyak V, Matulis VE, Zhel-
dakova RA, Lesnikovich AI, Ivashkevich OA (2011) J Phys
Chem C 115:16928
3
3
5. Zhu Y, Ren Y, Cai C (2009) Helv Chim Acta 92:171
6. Yapuri U, Palle S, Gudaparthi O, Narahari SR, Rawat DK,
Mukkanti K, Vantikommu J (2013) Tetrahedron Lett 54:4732
7. Gladysz JA (2001) Pure Appl Chem 273:1319
3
3
8. Islam M, Mondal P, Tuhina K, Roy AS, Mondal S, Hossain D
51. Ding R, Hu Y, Gui Z, Zong R, Chen Z, Fan W (2003) Polym
Degrad Stab 81:473
(2010) J Organomet Chem 695:2284
3
4
4
4
9. Islam SM, Mondal P, Roy AS, Mondal S, Hossain D (2010)
Tetrahedron Lett 51:2067
0. Tajbakhsh M, Heravi MM, Mohajerani B, Ahmadi AN (2006) J
Mol Catal A: Chem 247:213
1. Tajbakhsh M, Bazzar M, Ramzanian SF, Tajbakhsh M (2014)
Appl Clay Sci 88:178
2. Tajbakhsh M, Mohajerani B, Heravi MM, Ahmadi AN (2005) J
Mol Catal A: Chem 236:216
52. Rahman M, Roy A, Ghosh M, Mitra S, Majee A, Hajra A (2014)
RSC Adv 4:6116
53. Coca A, Turek E (2014) Tetrahedron Lett 55:2718
54. McManus JM, Herbst RM (1959) J Org Chem 24:1462
55. Popova EA, Pavlyukova YN, Popov EV, Ostrovskii VA, Tri-
fonov RE (2009) Russ J Org Chem 45:890
1
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