Synthesis, characterization, and investigation of catalytic activity of copper(II) porphyrin graphene oxide for azide–alkyne cycloaddition

Article abstract of DOI:10.1007/s11164-019-03843-y

Abstract: A covalently cross-linked graphene oxide (GO) catalyst was prepared by a cross-linking process using nucleophilic reaction of copper(II)‐coordinated 5,10,15,20-tetrakis(aminophenyl)porphyrin (CuPPh) with carboxyl groups at the edges of GO (GO–CuPPh). The structure of the catalyst was characterized using different techniques such as Fourier-transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive x-ray spectroscopy (EDS), thermogravimetric analysis (TGA), and inductively coupled plasma (ICP) spectroscopy. All analyses confirmed successful covalent immobilization of CuPPh on GO. The activity of the catalyst was then studied for synthesis of 1,4-disubstituted 1,2,3-triazoles derivatives by reaction of various aryl azides and different terminal alkynes in mild reaction condition with good to excellent yield. Graphical abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s11164-019-03843-y

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-019-03843-y
Synthesis, characterization, and investigation of catalytic
activity of copper(II) porphyrin graphene oxide
for azide–alkyne cycloaddition
Amir Khojastehnezhad, et al. [full author details at the end of the article]
Received: 20 January 2019 / Accepted: 28 April 2019
© Springer Nature B.V. 2019
Abstract
A covalently cross-linked graphene oxide (GO) catalyst was prepared by a
cross-linking process using nucleophilic reaction of copper(II)‐coordinated
5,10,15,20-tetrakis(aminophenyl)porphyrin (CuPPh) with carboxyl groups at the
edges of GO (GO–CuPPh). The structure of the catalyst was characterized using
diferent techniques such as Fourier-transform infrared (FT-IR) spectroscopy, scan-
ning electron microscopy (SEM), transmission electron microscopy (TEM), energy-
dispersive x-ray spectroscopy (EDS), thermogravimetric analysis (TGA), and induc-
tively coupled plasma (ICP) spectroscopy. All analyses confrmed successful covalent
immobilization of CuPPh on GO. The activity of the catalyst was then studied for syn-
thesis of 1,4-disubstituted 1,2,3-triazoles derivatives by reaction of various aryl azides
and diferent terminal alkynes in mild reaction condition with good to excellent yield.
Graphical abstract
Keywords Porphyrin · Copper · Graphene oxide · 1,2,3-Triazole · Click chemistry
Vol.:(0123456789)
1 3

A. Khojastehnezhad et al.
Introduction
Metal porphyrins (MPPhs) ofer various advantages, one of which is their potential
application as catalysts in organic reactions [1]. However, MPPhs are unstable and
difcult to reuse, and decompose easily in the presence of inert substrates [2], which
limits their use in industrial processes. These difculties can be overcome by immo-
bilization on heterogeneous supports. Solid supports can improve the catalytic activ-
ity of MPPhs by enabling easy separation and reusability.
Graphene oxide (GO) is a single layer of graphite that is prepared by oxida-
tion reactions and ofers unique properties [3]. GO has diferent functional groups
(hydroxyl and epoxide on basal plane, carboxyl at the edges of sheets) on its surface,
enabling further chemical reactions and surface functionalization [4]. Such materi-
als show interesting applications as catalysts and supports of various materials for
preparation of heterogeneous catalysts [5].
Huisgen introduced the 1,3-dipolar cycloaddition reaction of azides and alkynes
[6]. This catalyst-free reaction generally produces both triazole isomers (1,4- and
1,5-), making it inappropriate for organic syntheses. In 2002, Tornøe et al. [7] and
Rostovtsev et al. [8] reported the use of copper for this reaction under mild condi-
tions [9]. Recently, this method has become a popular route for synthesis of tria-
zoles using various homogeneous and heterogeneous catalysts such as Cu(OAc)2
[10], CuSO4·5H2O [11], nanosized CuO [12], silica-supported Cu nanoparticles
[13], nanomagnetic supported Cu nanoparticles [14], thiourea-supported copper(I)
chloride [15], and copper/carbon nanoparticles [16]. However, many of these meth-
ods have disadvantages that need to be addressed. Hence, the use of new and green
methods is still desirable and much in demand.
In previous study, for the frst time, we prepared nickel-porphyrin attached to GO
and studied its catalytic activity for the Suzuki–Miyaura cross-coupling reaction
[17]. In the work reported herein, the copper ion was inserted into the porphyrin
ring and the prepared Cu(II)-tetrakis(aminophenyl)porphyrin (Cu–PPh) was cova-
lently immobilized onto GO to synthesize the fnal catalyst GO–CuPPh (Scheme 1).
After complete characterization, the activity of the catalyst was studied in synthesis
of 1,4-disubstituted 1,2,3-triazoles via “click” chemistry (Scheme 2).
Experimental
General
Melting points of products were analyzed using an Electrothermal 9200 melting point
apparatus. FT-IR spectra were recorded using a Nicolet Avatar 370 FT-IR spectrom-
eter. Nuclear magnetic resonance (NMR) spectra were obtained with a Bruker Avance
instrument at 300 MHz in CDCl3. Transmission electron microscopy (TEM) was per-
formed with a Leo 912AB (120 kV) microscope (Zeiss, Germany). Inductively coupled
plasma optical emission spectroscopy (ICP-OES) analysis was carried out with a Var-
ian VISTA‐PRO, CCD (Australia). Elemental compositions were determined by EDX
1 3

Synthesis, characterization, and investigation of catalytic…
Scheme 1 Synthesis of graphene oxide copper-coordinated 5,10,15,20-tetrakis(aminophenyl)porphyrin
(GO–CuPPh)
Scheme 2 Synthesis of
1,2,3-triazole in presence of
catalyst (GO–CuPPh)
analysis (model 7353, Oxford Instruments, UK) with 133 eV resolution. TGA was per-
formed using a Shimadzu thermogravimetric analyzer (TG‐50) under air atmosphere at
heating rate of 10 °C min−1.
Preparation of GO–PPh
GO and PPh were prepared according to literature [18, 19]. For synthesis of GO–PPh,
GO–COCl (1.0 g) and synthesized porphyrin (0.5, 1.0 or 2.0 g) in dimethylformamide
(DMF, 100 mL) were taken in a round-bottomed fask, and triethylamine (30 mL) was
added followed by heating to 80 °C for 72 h under nitrogen atmosphere and an addi-
tional 1 h with intermittent sonication to give a homogeneous black dispersion. After-
wards, the resulting black mixture was permitted to cool to room temperature then
poured into diethyl ether (300 mL) to precipitate the product. The black precipitate was
collected by centrifuging at 8000 rpm for 30 min. The supernatant containing unre-
acted ligand was discarded. Finally, further diethyl ether (200 mL) was added and the
mixture was centrifuged at 8000 rpm for 30 min, and the immobilized ligand on GO
was collected.
1 3

A. Khojastehnezhad et al.
Preparation of GO–CuPPh
The complex of copper and GO–PPh was prepared by adding copper acetate
(0.5, 1.0 or 2.0 g) into the solution of GO–PPh (1.0 g) and 80 mL dimethylfor-
mamide. For complete metallation, the reaction mixture was refuxed for 8 h.
The obtained GO–CuPPh was collected by centrifuging at 8000 rpm for 30 min.
Finally, 20 mL water was added and the mixture was centrifuged at 8000 rpm for
30 min, and the obtained Cu–PPh on GO was collected.
General procedure for preparation of 1,2,3‑triazole derivatives 3a–n
To a solution of azide (1.10 mol) and terminal alkyne (1.0 mol) in a mixture of
H2O/EtOH (1:1; 2 mL), GO–CuPPh catalyst (5.0 mg) was added and the mixture
was irradiated at 60 °C for 5–30 min. Reaction progress was monitored by thin-
layer chromatography (TLC) and upon reaction completion, the reaction mixture
was diluted with EtOAc and the catalyst was centrifuged, and separated from the
reaction mixture. The organic layer was dried over anhydrous Na2SO4, followed
by evaporation under reduced pressure to remove the solvent. The residue was
purifed by recrystallization from ethanol to aford corresponding 1,4-disubsti-
tuted 1,2,3-triazoles. The product was identifed by melting point, 1H-NMR, and
13C-NMR spectroscopy.
1‑(4‑Diphenyl)‑1H‑1,2,3‑triazole (Table 2, entry 1) Pale-yellow solid, m.p. 97–98 °C.
1H-NMR (300 MHz, CDCl3): δ=7.28–7.81 (m, 6H), 7.93 (d, J=6.9 Hz, 2H), 8.22
(d, J=5.4 Hz, 2H), 8.52 (s, 1H); 13C-NMR (75 MHz, CDCl3): δ=148.3, 136.9,
130.1, 129.6, 128.8, 128.6, 128.3, 125.7, 120.4, 117.5.
1‑(4‑Bromophenyl)‑4‑phenyl‑1H‑1,2,3‑triazole (Table 2, entry 3) White solid, m.p.
232–234 °C. 1H-NMR (300 MHz, CDCl3): δ=7.35–7.91 (m, 9H), 8.17 (s, 1H); 13C-
NMR (75 MHz, CDCl3): δ=117.2, 121.7, 122.3, 125.7, 128.5, 128.7, 128.8, 129.8,
130.8, 132.8, 135.9.
1‑Benzyl1‑4‑phenyl‑1H‑1,2,3‑triazole (Table 2, entry 12) White solid, m.p. 128–
130 °C. H-NMR (300 MHz, CDCl3): δ=5.53 (s, 2H), 7.26–7.41 (m, 6H), 7.69 (s,
1H), 7.79–7.82 (m, 4H); 13C-NMR (75 MHz, CDCl3): δ=54.1, 119.7, 125.7, 128.0,
128.2, 128.7, 128.8, 129.1, 130.6, 134.7, 148.1.
(1‑Benzyl‑1H‑1,2,3‑triazol‑4‑yl) methanol (Table 2, entry 13) White solid, m.p.
75–76 °C. 1H-NMR (300 MHz, CDCl3): δ=2.50 (s, 1H), 4.52 (s, 2H), 5.50 (s, 2H),
7.40–7.31 (m, 5H), 8.02 (s, 1H); 13C-NMR (75 MHz, CDCl3): δ=148.7, 136.6,
129.1, 128.5, 128.3, 123.2, 55.5, 53.1.
1 3

Synthesis, characterization, and investigation of catalytic…
Results and discussion
The catalyst (GO–CuPPh) was synthesized according to the method described in
Scheme 1, using GO and porphyrin molecule prepared according to literature [18,
19]. To confrm preparation of the catalyst, it was fully characterized using vari-
ous techniques including FT-IR spectroscopy, SEM, TEM, EDS, TGA, and ICP
spectroscopy.
FT-IR spectroscopy (Fig. 1) revealed a broad absorption band at 3407 cm−1,
attributed to O–H stretching bands of hydroxy and carboxylic acid groups on the
edges and basal plane of GO. Also, for the GO structure, C=O, C=C, and C–O
groups appeared at 1716, 1587, and 1222 cm−1, respectively (Fig. 1a) [20]. In the
FT-IR spectrum of PPh (Fig. 1b), two broad bonds at 3313 and 3359 cm−1 corre-
spond to N–H bonds of pyrrole and NH2 groups of phenyl moieties. Figure 1c shows
the FT-IR spectrum of GO–PPh; the new band appearing at around 3388 cm−1 was
ascribed to stretching vibrations of N–H of PPh ligand, and the band related to C=O
was shifted to 1600 cm−1. The FT-IR spectrum after the metallation step did not
show any diferences (Fig. 1d). The results of this analysis confrm successful cova-
lent linkage of porphyrin on GO [18].
SEM, TEM, and EDS techniques were used to study the morphology, size, and
elemental content, respectively (Fig. 2). SEM of GO revealed layers of GO with
uniform surface, composed of sheet-like and transparent structures. SEM and TEM
images of the fnal catalyst (GO–CuPPh) are shown in Fig. 2b and c respectively,
both confrming successful covalent linkage of copper to porphyrin on the edges of
GO [18]. However, these images also show some CuPPh noncovalently immobilized
on the surface of GO via π–π stacking of aromatic moieties of PPh with sp2 carbons
of GO [21, 22]. Moreover, the presence of all elements (copper, chlorine, oxygen,
and carbon) in the structure of the catalyst was confrmed by EDS analysis (Fig. 2d).
TGA analysis was applied to confrm the high thermal stability of the cata-
lyst. As shown in Fig. 3, two main weight losses were observed. The frst began
at about 50 °C and continued until about 300 °C, being attributed to removal of
Fig. 1 FT-IR spectra of a GO,
b PPh, c GO–PPh, and d GO–
CuPPh
1 3

A. Khojastehnezhad et al.
Fig. 2 a SEM image of GO, b SEM image of GO–CuPPh, c TEM image of GO–CuPPh, and d EDS pat-
tern of GO–CuPPh
physically and hydrogen-bonded water and decomposition of hydroxyl, carboxyl,
and epoxy groups on the edges and basal plane of GO. The second between 300
and 750 °C is attributed to loss of PPh ligands immobilized on the GO moiety
[23].
The amount of copper in the fnal catalyst was studied by using the inductively
coupled plasma (ICP) technique. According to the results, the weight percentage
of Cu was 6.012 wt%, confrming successfully insertion of copper into the PPh
ring.
After characterization of the catalyst, the reaction conditions were optimized,
using the reaction of 4-nitrophenyl azide and phenylacetylene as a model reac-
tion (Table 1). The results demonstrated that the reaction did not proceed in
absence of catalyst in solvent-free condition, even after running the reaction for
24 h (entry 1). When the reaction was carried out in diferent polar and nonpo-
lar solvents (entries 2–5), the results were better in polar solvents such as water
and ethanol (entries 3, 4). We therefore examined mixtures of polar solvents with
various amounts of catalyst (entries 6–9). The reaction yield was higher in a mix-
ture of H2O/EtOH with ratio of 1:1 compared with H2O/MeOH (entries 6–8).
Also, the reaction produced high yield when using 5.0 mg (0.5 mol%) of catalyst
1 3

Synthesis, characterization, and investigation of catalytic…
Fig. 3 TGA of GO–CuPPh catalyst
Table 1 Optimization of solvent, temperature, and amount of catalyst
Entry Condition
Catalyst (mg, mol%) Temp. (°C) Time (h) TONa Yield (%)b
1
2
3
4
5
6
7
8
Solvent free (GO–CuPPh)
MeOH (GO–CuPPh)
H2O (GO–CuPPh)
EtOH (GO–CuPPh)
n-Hexane (GO–CuPPh)
H2O/MeOH (GO–CuPPh) 5.0, 0.5
H2O/EtOH (GO–CuPPh)
H2O/EtOH (GO–CuPPh)
H2O/EtOH (GO–CuPPh)
H2O/EtOH (GO–CuPPh)
H2O/MeOH (GO–CuPPh) 5.0, 0.5
H2O/EtOH (GO–CuPPh)
H2O/EtOH (GO–CuPPh)
–
rt
24
10
10
10
10
10
10
10
–
Trace
12
33
40
Trace
25
42
50
52
65
5.0, 0.5
5.0, 0.5
5.0, 0.5
5.0, 0.5
Refux
Refux
Refux
Refux
rt
rt
rt
rt
40
60
80
60
60
60
60
60
24
66
80
–
50
210
100
52
130
156
154
192
–
2.0, 0.2
5.0, 0.5
10, 1.0
5.0, 0.5
9
10
10
11
12
13
14
15
16
17
5.0
5.0
5.0
0.25
5.0
1.0
1.0
1.0
78
5.0, 0.5
5.0, 0.5
77
96c
Solvent-free (GO–CuPPh) 5.0, 0.5
H2O/EtOH (GO)
H2O/EtOH (PPh)
H2O/EtOH (GO–PPh)
Trace
None
None
None
5.0, –
5.0, –
5.0, –
–
–
–
aTurnover number
bBased on isolated yield
cUnder ultrasonic conditions
1 3

A. Khojastehnezhad et al.
Table 2 Optimization of diferent ratios of GO–COCl, PPh, and copper acetate in synthesis of catalyst
Entry
GO–COCl/PPh (g)
GO–PPh/Cu(OAc)2
Temp. (°C)
Time (h)
Yield (%)a
1
2
3
4
5
6
7
8
9
1.0:0.5
1.0:0.5
1.0:0.5
1.0:1.0
1.0:1.0
1.0:1.0
1.0:2.0
1.0:2.0
1.0:2.0
1.0:0.5
1.0:1.0
1.0:2.0
1.0:0.5
1.0:1.0
1.0:2.0
1.0:0.5
1.0:1.0
1.0:2.0
60
60
60
60
60
60
60
60
60
0.50
0.50
0.50
0.25
0.25
0.25
0.25
0.25
0.25
80
81
85
87
89
93
88
93
96
aBased on isolated yield
(entry 7–9), whereas further increase of the amount of catalyst did not noticeably
increase the yield (entry 9). Then, the reaction was studied at diferent tempera-
tures (entries 10–12), with the best result at 60 °C (entry 11), while the reaction
yield was unsatisfactory at higher or lower temperatures. Moreover, application
of ultrasound with the obtained conditions increased the reaction yield with about
20% shorter reaction time (entry 13). Finally, solvent-free condition in presence
of 0.5 mol% catalyst at 60 °C was also checked (entry 14), yielding trace product.
Thus, the best result was obtained when using 0.5 mol% catalyst at 60 °C with
ultrasound (entry 13). To show the efect of Cu element in the reaction, the role
of other parts of the catalyst such as GO, PPh, and GO–PPh (without Cu) was
also investigated in the model reaction under optimized conditions. The results
are presented in Table 1 (entries 15–17). As is evident, the reaction did not pro-
ceed when using the other parts of catalyst without Cu element, confrming that
the presence of Cu is essential to catalyze the reaction.
After fnding the optimized reaction condition, diferent ratios of GO–COCl,
PPh, and Cu source were optimized (Table 2). For this purpose, the catalyst was
synthesized using three diferent amounts of PPh and copper acetate (0.5, 1.0, and
2.0 g). The reaction yield was better when using twice the amount of copper acetate
to GO–PPh (entries 3, 6, and 9) and twice the amount of porphyrin to GO–COCl
(entries 6–9). Thus, the best result was obtained for GO–COCl/PPh (1:2) and
GO–PPh/Cu(OAc)2 (1:2) (entry 9).
The scope and generality of the method were investigated in the reaction of struc-
turally divergent azides and diferent terminal alkynes in presence of 0.5 mol% cat-
alyst (GO–CuPPh) (Table 3). All aryl azides carrying either electron-donating or
electron-withdrawing groups reacted successfully and led to formation of products
in high yield within short reaction time (5–30 min). Compared with phenyl azides,
benzyl azide required shorter reaction time (entries 12–14). Both aromatic and ali-
phatic terminal acetylenes gave corresponding 1,4-disubstituted 1,2,3-triazoles in
excellent yield and high purity.
According to literature [24, 25], a mechanism for the synthesis of 1,2,3-triazoles
catalyzed by copper-coordinated on GO–PPh is proposed in Scheme 3. In the frst
1 3

Synthesis, characterization, and investigation of catalytic…
Table 3 Synthesis of 1,2,3-triazoles 3a–n using GO–CuPPh as catalyst
Entry
R
R1
Producta
Time (min)
Yield (%)b
Melting point (°C)
Found
Reported
1
2
3
4
5
6
7
8
Ph
Ph
Ph
Ph
Ph
3a
3b
3c
3d
3e
3f
3g
3 h
3i
3g
3k
3l
3m
3n
15
15
18
20
30
15
30
15
30
20
30
5
92
96
91
95
96
90
92
88
89
92
91
95
93
96
97–98
97–98 [26]
254 [26]
232 [26]
174 [26]
228 [26]
116–118 [27]
201–202 [27]
135–137 [28]
124–125 [29]
144–145 [30]
152–154 [31]
129–131 [29]
75–77 [30]
124–126 [31]
4-NO2Ph
4-BrPh
4-CH3Ph
4-ClPh
Ph
4-NO2Ph
4-BrPh
4-CH3Ph
4-ClPh
4-NO2Ph
PhCH2
PhCH2
PhCH2
255–256
232–234
173–174
227–229
115–116
200–202
134–135
124–125
144–145
151–153
128–130
75–76
Ph
CH2OH
CH2OH
CH2OH
CH2OH
CH2OH
CH2Br
Ph
9
10
11
12
13
14
CH2OH
CH2Br
8
10
123–125
Reaction conditions: azides (2a–f; 1.1 mmol), terminal alkynes (2a–c; 1 mmol), GO–CuPPh (0.5 mol%)
at 60 °C in EtOH:H2O (1:1), and ultrasonic irradiation
aKnown products identifed by comparison of their melting points; some selected compounds character-
ized by 1H NMR and 13C-NMR
bIsolated yields
Scheme 3 Proposed mechanism
for synthesis of 1,2,3-triazoles
in presence of GO–CuPPh
step, a terminal alkyne is coordinated to Cu in the center of the porphyrin ligand,
which activates the C–H bond, then the corresponding copper–alkylidine com-
plex is formed. In the second step, aryl azides react with the copper–alkylidine
1 3

A. Khojastehnezhad et al.
Fig. 4 Reusability of catalyst in model reaction
Fig. 5 SEM image of catalyst
reused fve times
intermediate, followed by intramolecular cyclization to fnally produce the fve-
member ring of triazole as a product.
The reusability of the catalyst (GO–CuPPh) was investigated in the model reac-
tion. For this aim, after reaction completion, the catalyst was isolated from the reac-
tion mixture using simple centrifuging and washed completely with two solvents
(acetone and water) to remove residual product, dried at 100 °C under vacuum, and
reused in further reactions. The results showed the same activity as the fresh catalyst
without any signifcant loss of its activity (Fig. 4).
A SEM image of the 5th recovered GO–CuPPh is shown in Fig. 5. Interest-
ingly, no agglomeration or signifcant changes in the shape of the functionalized
GO (GO–CuPPh) were observed even after fve consecutive recycle runs. Also, the
FT-IR spectra of GO–CuPPh catalyst before use (fresh) and after reuse fve times
(recovered) were studied. As shown in Fig. 6, the FT-IR spectrum of the recovered
GO–CuPPh showed that the structure of the catalyst remained almost the same after
fve runs of reuse, confrming the stable structure of the catalyst.
1 3

Synthesis, characterization, and investigation of catalytic…
Fig. 6 FT-IR spectrum of catalyst: a fresh and b reused fve times
Table 4 Comparison of GO–CuPPh catalyst with other heterogeneous catalysts in synthesis of 1,2,3-tria-
zole 3a
Entry
Catalyst
Solvent
Temp. (°C)
Time (min)
Yield (%)a
Ref.
1
2
3
4
5
6
CuII–hydrotalcite
AgN(CN)2
CuSO4/urea
Cu(PPh3)2NO3
Nano-Cu/SiO2
GO–CuPPh
MeCN
H2O/EG
H2O
Solvent-free
DMSO
EtOH:H2O
rt
rt
rt
rt
rt
60
360
120
60
40
25
86
95
92
96
97
95
[32]
[33]
[11]
[34]
[35]
This study
15
aBased on isolated yield
In addition, to confrm the heterogeneous nature of the GO–CuPPh nanocata-
lyst, a hot fltration test was carried out during the model reaction under the opti-
mized condition. In this test, a mixture of 4-nitrophenyl azide (1.1 mmol), pheny-
lacetylene (1 mmol), and GO–CuPPh (0.5 mol%) at 60 °C in EtOH:H2O (1:1) was
irradiated at 60 °C for 8 min. After 50% conversion, the catalyst was separated
from the reaction mixture, then the reaction was continued for an additional time
(7 min). No further product formation was observed when monitored by TLC.
This result clearly demonstrates that no leaching of Cu or CuPPh took place dur-
ing the reaction, and the GO–CuPPh was truly heterogeneous in nature.
To confrm the merit of our study, use of GO–CuPPh in synthesis of 1,4-disub-
stituted 1,2,3-triazoles (phenyl azide and phenylacetylene) is compared with other
heterogeneous catalysts in Table 4. Based on the results, the presented catalyst
shows more satisfactory catalytic activity in shorter reaction time under milder
reaction conditions.
1 3

A. Khojastehnezhad et al.
Conclusions
A new cross-linked catalytic system was prepared by covalent and noncovalent
attachment of Cu(II)‐coordinated 5,10,15,20-tetrakis(aminophenyl)porphyrin to
GO. According to TEM and SEM images, in addition to at the edges, CuPPh was
also linked onto the basal plane of GO. The prepared catalyst was applied in syn-
thesis of 1,4-disubstituted 1,2,3-triazoles in short reaction time and high yield
under ultrasonic irradiation.
Acknowledgements The authors are grateful to the Iran National Science Foundation and Ferdowsi
University of Mashhad for fnancial support.
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Afliations
Amir Khojastehnezhad1 · Mehdi Bakavoli1 · Ali Javid2 ·
Mohammad Mehdi Khakzad Siuki1 · Mansour Shahidzadeh3
*
Amir Khojastehnezhad
akhojastehnezhad@yahoo.com
1
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad,
Mashhad 91775‐1436, Iran
2
3
Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran
Faculty of Chemistry and Chemical Engineering, Malek Ashtar University of Technology,
Tehran, Iran
1 3