Functionalized graphene oxide supported copper (I) complex as effective and recyclable nanocatalyst for one-pot three component synthesis of 1,2,3-triazoles

Article abstract of DOI:10.1002/aoc.3626

Efficient, one pot three-component reaction of alkyl halides, sodium azide with terminal alkynes can be catalyzed by functionalized graphene oxide with copper(I) under thermal conditions. A series of 1,4-disubstituted 1,2,3-triazoles were obtained by this one-pot strategy. The catalyst was prepared and characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray (EDX). The catalyst can be reused at least five times without significant deactivation.

Full text of DOI:10.1002/aoc.3626

Received: 10 August 2016
DOI 10.1002/aoc.3626
Accepted: 20 August 2016
F U L L PA P E R
Functionalized graphene oxide supported copper (I) complex as
effective and recyclable nanocatalyst for one‐pot three component
synthesis of 1,2,3‐triazoles
Hossein Naeimi | Rahele Shaabani | Mohsen Moradian
Department of Organic Chemistry, Faculty of
Efficient, one pot three‐component reaction of alkyl halides, sodium azide with ter-
Chemistry, University of Kashan, Kashan, Iran
minal alkynes can be catalyzed by functionalized graphene oxide with copper(I)
Correspondence
Hossein Naeimi, Department of Organic
under thermal conditions. A series of 1,4‐disubstituted 1,2,3‐triazoles were obtained
by this one‐pot strategy. The catalyst was prepared and characterized by Fourier
transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), emission
Chemistry, Faculty of Chemistry, University of
Kashan, Kashan, 87317, I.R. Iran.
Email: naeimi@kashanu.ac.ir
scanning electron microscopy (FE‐SEM) and energy dispersive X‐ray (EDX). The
catalyst can be reused at least five times without significant deactivation.
Funding Information
University of Kashan, 159148/66.
KEYWORDS
1,2,3‐triazole, graphene oxide, heterogeneous catalyst, one pot, three component
1
|
INTRODUCTION
In continuation of ongoing to our work toward click reac-
tion,[36,37] here we wish to report an efficient and safe one‐pot
synthesis of 1,4‐disubstituted 1,2,3‐triazoles from in situ
generated azides and terminal alkynes which were recyclably
catalyzed by heterogeneous copper(I) functionalized
graphene oxide under thermal condition at 70°C.
1,2,3‐Triazoles are typical five‐membered nitrogen heterocy-
clic compounds. They have a wide range of biological activ-
ities such as anti‐HIV activity,[1] anti‐microbial activity
against gram positive bacteria,[2] anti‐allergic,[3] antican-
cer,[4–6] β‐lactamase inhibitory,[7] selective β3 adrenergic
receptor agonism.[8] Additionally, 1,2,3‐triazoles have a
range of important applications in industries such as dyes,
corrosion inhibition, photostabilizers, photographic mate-
rials, and agrochemicals.[9] Several synthetic methods for
producing 1,2,3‐triazoles have been developed recently.
The most popular method for the synthesis of 1,2,3‐triazoles
is the Huisgen 1,3‐dipolar cycloaddition reaction of azides
with alkynes.[10,11] The Cu(I)‐catalyzed azide‐alkyne
cycloaddition (CuAAC),[12–15] one of the most reliable
“click reactions”,[16,17] has enabled the practical and
efficient preparation of 1,4‐disubstituted 1,2,3‐triazoles.
The required copper(I) catalysts are usually prepared by in
situ reduction of copper(II) salts with ascorbate,[18,19] or by
comproportionation of copper(0) and copper(II).[20,21]
Recently, graphene and graphene oxide have attracted
tremendous attention in the development of composite mate-
rials and catalysts,[22–32] due to their remarkable physical,
chemical and electrical characteristics, including a very high
specific surface area.[33–35]
2
| EXPERIMENTAL
2.1 | Materials
The chemical and materials used in this research were pur-
chased from Merck, Fluka, and Aldrich Chemical Compa-
nies. Alkyl halides and solvents were purified by use of
standard procedures.
2.2 | Apparatus
IR spectra were recorded as KBr pellets on a Perkin‐Elmer
781 spectrophotometer or an Impact 400 Nicolet FTIR spec-
trophotometer. 1H NMR and 13C NMR spectra were recorded
in CDCl3 solvent on a Bruker DRX‐400 spectrometer with
tetramethylsilane as internal reference. X‐ray diffraction
patterns of samples were taken on a Philips Xpert X‐ray
powder diffraction diffractometer (CuK, radiation,
k = 0.154056 nm). FE‐SEM and elemental analysis were
Appl Organometal Chem 2016; 1–7
wileyonlinelibrary.com/journal/aoc
Copyright © 2016 John Wiley & Sons, Ltd.
1

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NAEIMI ET AL.
carried out using a Jeol SEM instrument (model‐ VESCAN)
combined with an INCA instrument for energy dispersive
X‐ray scanning electron microscopy (EDX–SEM), Field
emission scanning electron microscopy (FE‐SEM) images
were obtained by HITACHI S‐4160. Melting points were
obtained with a Yanagimoto micro melting point apparatus
are uncorrected. The purity determination of the substrates
and reaction monitoring were accomplished by TLC on
silica‐gel polygram SILG/UV 254 plates (from Merck
Company).
2.7 | Synthesis of functionalized graphene oxide with
copper(I)(GO‐CONH‐IA‐Cu(I))
In the final step of catalyst preparation, GO‐CONH‐IA
(0.35 g) and copper iodide (0.35 g) was suspended in
30 mL acetonitrile and refluxed at 60°C for 18 h. The resul-
tant solution was filtered and washed with acetonitrile to
ensure that the excess copper iodide was completely
removed. Finally, the products were dried at 80°C under vac-
uum, the pure complex was obtained.
2.3 | Synthesis of graphene oxide (GO)
2.8 | A typical procedure for the synthesis of 1, 2,3‐
triazoles
Graphene oxide was prepared using a modification of
Hummers and Offeman's method.[38] Briefly in a typical
reaction, 2 g graphite, 1 g NaNO3, and 46 mL H2SO4 were
stirred together in an ice bath. KMnO4 (6 g) was slowly
added while stirring, and the rate of addition was controlled
to prevent the mixture temperature from exceeding 5°C. The
mixture was then transferred to a 35°C water bath and
stirred for about 30 min, forming a thick paste. Subse-
quently, 100 mL deionized water was added gradually and
the temperature was raised to 98°C. The mixture was further
treated with 500 mL deionized water and 15 mL 30% H2O2
solution. The warm solution was then filtered and dried at
65°C under vacuum. Finally, the precipitate was dispersed
in water by sonication.
Alkyne (1 mmol), alkyl halide (1 mmol), NaN3 (1.2 mmol)
and Cu(I) functionalized graphene oxide (0.01 g)as a catalyst
were added to a mixture of water and EtOH (1:1) (6 mL) and
stirred at 70°C. The progress of the reaction was monitored
by TLC. After completion of the reaction, the catalyst was
isolated by filtration through celite and the product was
extracted with EtOAc (3 × 10 mL). The products were char-
acterized by 1H NMR, 13C NMR, FT‐IR and melting
pointsand were carefully identified by comparison of their
spectral data with those of authentic samples.[39–44]
3
| RESULTS AND DISCUSSION
3.1 | Preparation and characterization of the catalyst
2.4 | Synthesis of GO–COCl
Synthesis strategy of functionalized graphene oxide is shown
in the Scheme 1. At first, graphene oxide was prepared
according to the modified Hummer's method. The obtained
GO was treated with thionyl chloride in DMF at reflux tem-
perature for 24 hours to generate GO–COCl and subsequently
reacted 1,7‐heptandiaminto yield amino‐modified graphene
oxide (GO‐CONH2). The obtained amino‐modified graphene
oxide were then treated with Isotoic anhydride in ethanol at
reflux temperature for 24 hours to generate (GO‐CONH‐IA).
Finally, the GO‐CONH‐IA was treated with CuI in acetoni-
trile at reflux temperature for 18 hours. The catalyst was
characterized using various methods.
Figure 1 shows the FTIR spectra of GO, GO‐COCl, GO‐
CONH2, GO‐CONH‐IA. In the FTIR spectrum of GO, the
peaks at 3349, 1719, 1580 and 1064 cm−1 correspond to
the O–H, C = O, C = C and C–O stretching vibration. In
the FTIR spectrum of GO–COCl (Figure 4b), the relative
intensity of the C = O stretch of the –COOH at 1730 cm−1
has significantly decreased that confirmed the most carboxyl
functionalities have been transformed into the acyl chloride.
Figure 2 shows XRD patterns of GO and GO‐CONH‐IA‐
Cu(I). The XRD pattern of GO (Figure 2a) shows an intense
and sharp peak centered at 11.99° which corresponds to an
interplanar distance of 0.78 nm. After the functionalization,
in the XRD patterns of GO‐CONH‐IA‐Cu(I), the peak at
In this step, GO (0.5 g) was suspended in SOCl2 (10 mL) and
10 mL of DMF was added and refluxed at 70°C for 24 h. The
resultant solution was filtered and washed with anhydrous
tetrahydrofuran (THF) and dried under vacuum, the
GO‐COCl was obtained.
2.5 | Synthesis of amino‐functionalized graphene oxide
(GO‐CONH2)
In this step of catalyst preparation, GO–COCl (0.4 g) and 1,7‐
heptandiamine was added in 25 mL DMF and refluxed at
75°C for 18 h. The resultant solution was filtered and
washed with ethanol to ensure that the excess diamine was
completely removed. Finally, the products were dried at
80°C under vacuum.
2.6 | Synthesis of functionalized graphene oxide with
Isotoic anhydride (GO‐CONH‐IA)
In continuation, GO‐CONH2 (0.36 g) and Isotoic anhydride
(0.36 g) were added in 30 mL ethanol and refluxed at 60°C
for 22 h. The resultant solution was filtered and washed with
ethanol to ensure that the excess Isotoic anhydride was
completely removed. Finally, the products were dried at
70°C under vacuum.

NAEIMI ET AL.
3
FIGURE 2 XRD patterns of (a) GO and (b) GO‐CONH‐IA‐Cu(I)
FIGURE 3 TGA and DTA graphs of the GO‐NH‐IA‐Cu
SCHEME 1 Preparation routes of functionalized graphene oxide
shown in Figure 3, the attached organic groups decomposed
at 200°C, while the GO remained stable up to 600°C, at
which temperature oxidation started. Accordingly, these
results indicate that about 31 wt% can be ascribed to the
covalency of organic groups. Results obtained by TGA
showed good agreement with results of FT‐IR spectroscopy.
The successful covalent grafting of NH‐IA‐Cu(I) onto the
surface of graphene oxide was further confirmed by EDX
analysis. EDX spectra of functionalized graphene oxide‐Cu
(I) is shown in Figure 4 and Table 1 that was confirmed the
presence of copper, iodine and nitrogen elements in the
complex structure (Table 1).
The FE‐SEM images of GO and GO‐CONH‐IA‐Cu(I) are
shown in Figure 5. As can be clearly seen in this Figure, the
GO has layered structures with sheets crumpled. Figure 5b is
indicated the SEM image of GO‐CONH‐IA‐Cu(I) revealing
that the layered structure can be maintained in the functional-
ized graphene oxide after the treatments.
FIGURE 1 FT‐IR spectra of a) GO, b) GO‐COCl c) GO‐CONH2 d) GO‐
CONH‐IA
about 2 = 23.7 o was broad peak. The reasons of this matter
can be due to the covalent bond functionalization.
3.2 | Investigation of the catalyst activity
TGA thermograms were used to confirm the anchoring of
organic groups on the surface of GO. As shown in Figure 3,
the weight loss (9%) before 160°C is caused by the release of
trapped water between GO nanosheets. Also, weight loss
between 200 and 600°C is completely due to functional
groups on the surface of graphene oxide nanosheets. As
In order to optimization of the reaction conditions, the reac-
tion of alkyne (1 mmol), alkyl halide (1 mmol) and NaN3
(1.1 mmol) were studied as a simple model. The reaction
was carried out in the presence of different quantities of the
catalyst in water‐ethanol solvent (Table 2). It was found that

4
NAEIMI ET AL.
TABLE 2 Optimization of catalyst for synthesis of 1,2,3‐triazole
Entry
Catalyst (g)
Time (h)
Yield (%)a
1
2
3
4
0.005
0.010
0.015
0.020
3
1
1
1
87
90
87
84
aIsolated yields
Reaction conditions: 1 mmol phenylacetylene, 1 mmol benzyl chloride, 1.1 mmol
NaN3, and selected solvent (6 mL) at 70°C temperature
FIGURE 4 EDX spectra of GO‐CONH‐IA‐Cu(I)
TABLE 1 Elemental analysis of GO‐CONH‐IA‐Cu(I)
TABLE 3 The preparation of triazols in the presence of various solvents
Entry
Solvent
CH3CN
Time (h)
Yield (%)a
Element
C
O
N
Cu
1
2
3
4
5
6
5
55
62
75
90
84
68
%W
54.21
17.67
17.37
0.73
H2O‐CH3CN(1:1)
H2O‐Acetone(1:1)
H2O‐EtOH(1:1)
EtOH
4.5
4
1
3
H2O
3.5
aIsolated yields
Reaction conditions: 1 mmol phenylacetylene, 1 mmol benzyl chloride, 1.1 mmol
NaN3, and selected solvent (6 mL) at 70°C temperature.
To check the influence of temperature on the yield of the
triazole product, we carried out model reaction at various
temperatures in the range of 35°C to 80°C (Table 4), showing
that at 70°C, the yield of the product was maximized to 90%
(Table 4, entry 3). A further increase in temperature had no
profound effect on the yield of the reaction (Table 4).
After optimization of the reaction conditions, the reaction
was carried out according to the general experimental proce-
dure shown in Scheme 2.
In order to development and limitations of the general
method, we investigated the reaction, using a variety of benzyl
and alkyl halides and alkynes as the substrates under the same
conditions. The related results are summarized in Table 5.
The regarding results were shown that in the presence
of this new solid heterogeneous catalyst, the 1,2,3‐triazole
TABLE 4 Effect of temperature on synthesis of 1,2,3‐triazole
Entry
Temperature
Time (h)
Yield (%)a
1
2
3
4
35
50
70
80
3
86
87
90
88
2
FIGURE 5 FE‐SEM of (a) GO, (b) GO‐CONH‐IA‐Cu(I)
1
1.5
aIsolated yields
the best result was obtained when the reaction was carried out
in the presence of 0.01 g of catalyst (Table 2, entry 2).
In order to verify the effect of solvent, the model reaction
was carried out in the presence of different solvents. The
corresponding results are shown in Table 3. The best solvent
was1:1 mixture of H2O and EtOH, which was resulted in
higher yield and shorter reaction time in compared to other
solvents (Table 3, entry 4).
SCHEME 2 Synthesis of 1,4‐disubstituted 1,2,3‐triazoles

NAEIMI ET AL.
5
TABLE 5 Preparation of 1,2,3‐triazoles from the reaction of alkyl halides, acetylenes, and sodium azide catalyzed by GO‐NH‐IA‐Cu(I)
Entry
R1
R2
Product
Time (h)
Yielda (%)
1
Bn
Ph
1
90
2
4‐Br‐Bn
Ph
1.5
89
3
4
3‐Cl‐Bn
2‐Cl‐Bn
Ph
Ph
2
87
86
2.5
5
6
2‐Cl‐6‐F‐Bn
Ph
Ph
3
83
82
2,4‐(NO2)2‐Bn
3.5
7
8
9
Bn
P‐CH3‐Ph
P‐CH3‐Ph
Ph
3.5
4
92
94
85
4‐Br‐Bn
CH3
7
10
11
4‐NO2‐Bn
4‐NO2‐Bn
Ph
2
4
88
89
P‐CH3‐Ph
12
13
Bn
CH3‐(CH2)2
8
5
78
88
Cinamyl
Ph
aIsolated yields
products were yielded in excellent within a very short reac-
tion times. In order to show the merit of this study, we
compared the obtained results with the recently reported
works[45–52] in Table 6. The comparison was carried out
on the basis of reaction conditions, reaction time, and
yields of the products.
phase was subjected as solvent to further reaction with the
new three substrates of starting materials without using any
catalyst and carried out under the modified reaction condi-
tions. After the suitable time, the reaction was analyzed and
was observed that there was no further conversion of moieties
to triazole product when the catalyst was removed. The reac-
tion cannot progress, and a negligible product was obtained
(<2%) after 25 h reaction time. It is notable that the active
catalyst did not leach from the GO as the solid supporter.
Also, the final reaction media was analyzed by using atomic
absorption spectroscopy and the resulted was observed that
3.3 | The study of leaching and reusability of the
catalyst
For catalyst leaching study, after completion of the reaction,
the solid catalyst was separated by celite filter. The liquid

6
NAEIMI ET AL.
TABLE 6 Comparison of triazole synthesis by using GO‐CONH‐IA‐Cu (I) with literature reported methods
Entry
Catalyst
[CuBr(PPh3)3]
Reaction conditions
0.5 mol% cat., H2O, r.t.
Time /Yield [Lit.]
[45]
1
8 h/88%
[46]
2
CuI/DIPEA/HOAc
2 mol % CuI, CH2Cl2, r.t.
2 mol % cat., H2O, r.t.
2 h / 91%
[47]
3
Copper(I) Isonitrile Complex
4 h / 92%
[48]
4
1.5 equation ZnEt2, 0.1 eq. N‐methylimidazole, THF, r.t.
1 eq. CuCl, 2.5 mol% Pd2(dba)3, DMF, 70°C
18 h / 76%
[49]
5
CuCl/Pd2(dba)3
2 h / 89%
[50]
6
poly(imidazole‐acrylamide):CuSO4
Cu‐apatite
0.25 mol % cat., t‐BuOH, 50°C
5 mol % cat., H2O, 100°C
0.10 g cat., 100°C
2.5 h, 90%
[51]
7
1.5 h / 85%
[52]
8
9 a
Cu(OAc)2/MCM‐41
GO‐CONH‐IA‐Cu(I)
2 h / 88%
0.01 g cat., H2O‐EtOH(1:1), 70°C
1 h / 90%
aPresent study
leaching of the Cu metal from the GO, was less than 0.1% by
weight of the initial copper metal.
purification. Also, it could be recycled in six repetitive cycles
without significant loss of activity (Figure 6). Moreover, the
SEM image of recycled catalyst after fifth run was provided
(Figure 7) in that indicated any changing in the structure of
catalyst after the reactions.
The recyclability of functionalized graphene oxide‐Cu(I)
catalyst was tested in the cycloaddition of benzyl chloride,
NaN3 and phenylacetylene under the optimized reaction con-
ditions. After the completion of reaction, the catalyst was sep-
arated by filtration and washed with acetone and water. After
drying, the catalyst could be reused directly without further
4
| CONCLUSIONS
In this research, we have presented a new heterogeneous cat-
alyst for the one‐pot regiospecific synthesis of 1,4‐disubsti-
tuted1,2,3‐triazoles via Huisgen 1,3‐dipolar cycloaddition
reaction between terminal alkynes, halides and NaN3 in the
presence of GONH‐IA‐Cu(I). In addition, the catalyst could
be readily recovered and reused for 5 cycles without signifi-
cant loss of its activity.
ACKNOWLEDGMENTS
The authors are grateful to University of Kashan for
supporting this work by Grant No. 159148/66.
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SUPPORTING INFORMATION
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