Cellulose supported cuprous iodide nanoparticles (Cell-CuI NPs): A new heterogeneous and recyclable catalyst for the one pot synthesis of 1,4-disubstituted-1,2,3-triazoles in water

Article abstract of DOI:10.1039/c4ra05080k

Cellulose supported cuprous iodide nanoparticles (Cell-CuI NPs) have been demonstrated for the first time as an efficient heterogeneous catalyst in the click synthesis of 1,4-disubstituted 1,2,3-triazoles by a one-pot three component reaction between aral

Full text of DOI:10.1039/c4ra05080k

RSC Advances
View Article Online
View Journal | View Issue
PAPER
Cellulose supported cuprous iodide nanoparticles
(Cell-CuI NPs): a new heterogeneous and
recyclable catalyst for the one pot synthesis of 1,4-
disubstituted – 1,2,3-triazoles in water†
Cite this: RSC Adv., 2014, 4, 42137
a
a
a
Pramod V. Chavan, Kapil S. Pandit, Uday V. Desai, Makarand A. Kulkarnia
*
and Prakash P. Wadgaonkarb
Cellulose supported cuprous iodide nanoparticles (Cell-CuI NPs) have been demonstrated for the first time
as an efficient heterogeneous catalyst in the click synthesis of 1,4-disubstituted 1,2,3-triazoles by a one-pot
three component reaction between aralkyl/alkyl bromides, alkynes and sodium azide in water. The catalyst
has been characterized by XRD, HRTEM, SEM, ICP–AES, EDS as well as IR spectroscopy. It was found to be
reusable for five consecutive runs without significant loss of activity.
Received 29th May 2014
Accepted 22nd August 2014
DOI: 10.1039/c4ra05080k
www.rsc.org/advances
applications, synthesis of 1,2,3-triazoles is receiving increased
attention.
Introduction
For the synthesis of 1,2,3-triazoles several approaches are
available.12 However, thermally induced 1,3-dipolar cycloaddi-
tion between alkynes and azides is the most preferred
pathway.13 In overcoming few of the limitations associated with
this cycloaddition protocol, Sharpless as well as Meldal intro-
duced Cu(I) catalysed synthesis of 1,2,3-triazoles.14a,b Develop-
ment of copper catalysed azide alkyne cycloaddition (CuAAC)
proved to be an important milestone in the synthesis of 1,2,3-
triazoles15,16 and plethora of protocols were subsequently
reported for their synthesis.17–27 It is worthy to note that, most of
these protocols, with variation in the nature of copper source,
were two-component protocols involving the reaction between
pre-synthesized azides and alkynes. In light of the well docu-
mented advantages of one-pot reactions and the difficulties
associated with handling of low molecular weight azides,
Appukkuttan et al. and Feldman et al. reported one-pot, three
component synthesis of triazoles using copper (0)-copper(II) and
With the growing concern over environmental protection a
great deal of attention has recently been focused on the devel-
opment of green synthetic methodologies. In this context, the
coupling of three or more components in a single step, the use
of eco-benign solvents and the selection of a heterogeneous and
reusable catalysts can be looked upon as three corners of an
equilateral triangle representing green chemistry.1 In particular,
the last decade has witnessed tremendous developments in the
eld of heterogeneous catalysis.2a One important development
in the eld of heterogeneous catalysis is nano-catalysis.2b This is
because nano catalysts, while retaining their intrinsic proper-
ties, are known to offer advantages as regards improvement in
reactivity, selectivity as well as yields. Thus, design of a novel
nano catalyst and exploration of it's catalytic potential in the
synthesis of compounds having diverse applications is an
attractive area of research.
1,2,3-Triazoles constitute an important class of heterocycles
having diverse applications in the eld of material science as
well as pharmaceutical chemistry.3–6 Many compounds con-
taining 1,2,3-triazole structural motif are known to possess
important biological activities such as anti-viral, anti-epileptic,
anti-allergic, anti-cancer, anti-microbial as well as anti-HIV
activities.7–10 In addition, compounds belonging to this class
are also useful as dyes, corrosion inhibitors, photographic
materials, photo sensitizers, etc.11 Owing to such a wide range of
copper(II)
– sodium ascorbate combination as catalysts,
respectively.28a,b These reports in fact opened a new door for
copper catalysed one-pot synthesis of 1,2,3-triazoles. Thus,
many modied protocols, mainly aimed at recovery and reuse of
copper catalyst, were subsequently reported.29a,b With recent
advances in the eld of nano catalysis and aer the discovery
that, transition metal nano particles do serve as efficient cata-
lysts,30a,b copper nanoparticles supported on alumina,31a CuI–Cu
nanoparticles on activated carbon,31b copper-NPs on activated
carbon,31c
CuFe2O4
nanoparticles,32a
graphene-g-Fe2O3
magnetic nanoparticles,32b Cu–SiO2 composites,33a Cu2O nano
crystals,33b CuBr supported on Oyster Shell Powder,34a CuBr
supported on graphene oxide/Fe3O4,34b Cu(II) PBS bridged
HPMOs,34c silica immobilised NHC-CuI,35a Cu1-Zeolite,35b P4VPy-
aDepartment of Chemistry, Shivaji University, Kolhapur, 416 004, India
bPolymer Science and Engineering Division, CSIR National Chemical Laboratory, Pune,
411 008, India. E-mail: uvdchem2011@gmail.com; Fax: +91-0231-2692333
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c4ra05080k
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 42137–42146 | 42137

View Article Online
RSC Advances
Paper
Cellulose is a naturally occurring biopolymer abundantly
available in nature and serves as a bio-compatible support for
the catalysts. Literature survey revealed that, Xu et al. have
reported the use of cellulose supported Pd in Heck reaction38
while Reddy et al. have reported the use of cellulose supported
Cu (0) as catalyst in aza-Michel reaction.39 In this article, we
report the synthesis as well as use of cellulose supported CuI
nanoparticles (Cell-CuI NPs) as a new catalyst in one-pot
synthesis of 1,2,3-triazoles (Scheme 1).
Scheme 1 Cell-CuI-NPs catalysed synthesis of 1,2,3-triazoles.
CuI nanoparticles,35c Cu(II)-TD@nSiO2,36a g-Fe2O3/HAP nano-
particles,36b etc. have been reported in one-pot synthesis of 1,4-
disubstituted ꢀ1,2,3-triazoles. Most of these protocols are
although efficient, a few of them suffer from the drawbacks of
tedious preparation of the catalyst, high reaction temperature,
longer reaction time, etc. With these observations in mind and
in tune with our continued interest in the development of green
synthetic methodologies37 we surmised that, there certainly
exists scope for the development of a green and easily adaptable
protocol for the synthesis of 1,2,3-triazoles. At the same time it
was quite evident that, for the known synthesis of a target
molecule, the main variant in practicing its green synthesis
should essentially be aimed at the design of an easy to prepare,
efficient, bio-compatible and reusable catalyst.
Results and discussion
A simple method was developed for the preparation of cellulose
supported CuI catalyst. In a typical procedure, to a stirred
suspension of CuI (0.190 g, 1 mmol) in methanol (30 mL) was
Fig. 3 SEM images of Cell – CuI. Before reaction: (a) 10 mm, (b) 20 mm;
after reaction (c) 10 mm, (d) 20 mm.
Fig. 1 EDS spectrum of Cell-CuI.
Fig. 2 XRD analysis of (a) CuI (b) cellulose and (c) cellulose supported Fig. 4 HRTEM images of Cell-CuI on (a) 50 nm (b) 200 nm (c) 1 mm (d)
CuI.
SAED.
42138 | RSC Adv., 2014, 4, 42137–42146
This journal is © The Royal Society of Chemistry 2014

View Article Online
Paper
RSC Advances
using Scherer's formula. The peak of highest intensity [25.5ꢁ (1,
1, 1)] was selected to evaluate the particle diameter of CuI and it
was found to be 33 nm. The average size of CuI particles on
cellulose was estimated to be 28 nm. SEM image of the prepared
catalyst indicated the deposition of nano-sized CuI crystals on
cellulose (Fig. 3a and b). This reveals that, during preparation of
the catalyst, possibly due to very low solubility of CuI in meth-
anol, CuI gets converted to nano sized CuI and gets deposited
over the surface of cellulose. HRTEM image of Cell-CuI (Fig. 4a–
c) further conrms the presence of CuI on cellulose support
with particle size 20–25 nm. SAED image (Fig. 4d) in HRTEM
shows different lattice fringes which matches well with different
planes of CuI according to XRD pattern.
Fig. 5 FT-IR spectra of (a) cellulose and (b) cellulose supported CuI.
added microcrystalline cellulose (2 g) and stirring was
continued overnight. The reaction mixture was ltered and the
residue was washed repeatedly with methanol and nally with
acetone. It was dried in air and then at 50 ꢁC for six hours under
vacuum. The resultant catalyst (Cell-CuI NPs) was characterised
by XRD, HRTEM, SEM, ICP-AES, EDS, and FT-IR spectroscopy.
Copper content in the prepared catalyst was estimated by
ICP-AES technique and it was found to be 2.4% (w/w). EDS
image (Fig. 1) of the catalyst indicated the presence of CuI
supported on cellulose. The analysis also conrmed the pres-
ence of CuI on support as its respective energy position at 0.92
keV (L line) and 8.04 keV (K line).
XRD pattern of CuI and cellulose supported CuI (Fig. 2a and
c) showed eight peaks at 2q ¼ 25.5ꢁ, 29.5ꢁ, 42.2ꢁ, 50.0ꢁ, 61.2ꢁ,
67.45ꢁ, 77.20ꢁ, 82.8ꢁ. All the diffraction peaks and their posi-
tions for CuI, match well with JCPDS card (no. 01-076-0207) for
cubic CuI. The crystallite size of CuI in Cell-CuI was determined
Scheme 2 Plausible mechanism of formation of 1,2,3-triazoles.
Table 1 Optimization of the reaction conditions for one-pot synthesis of 1,2,3-triazole, 3a, using Cell-CuI as catalysta
No.
Reaction medium
Catalyst (mg)
Temperature (ꢁC)
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
9
10
Water
Ethanol
Acetonitrile
Tetrahydrofuran
Toluene
Dichloromethane
Dimethylformamide
Acetonitrile + water (1 : 1)
Acetonitrile + water (1 : 3)
t-Butanol + water (3 : 1)
200, 150, 100, 75, 50
200, 150, 100
200, 150, 100
200
200
200
200
200
200
200
100, 90, 80, 70, 60
Reux
Reux
Reux
100
Reux
100
Reux
Reux
3, 3, 3, 3, 5
4, 4, 4
4, 4, 4
5
5
5
5
5
5
5
95, 94, 94, 84, 79
86, 85, 82
76, 73, 69
37
67
42
61
78
83
73
Reux
a
Reaction conditions: benzyl bromide (1 mmol), phenyl acetylene (1 mmol), sodium azide (1. 1 mmol), solvent, catalyst, temperature. b Yields refer
to isolated product.
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 42137–42146 | 42139

View Article Online
RSC Advances
Paper
Comparison of the FT-IR spectra of cellulose and cellulose spectrum of cellulose supported CuI (Fig. 5b) exhibits a char-
supported CuI indicated that, when CuI gets supported on acteristic band at 670 cmꢀ1 indicating the presence of copper.
cellulose intensity of broad band due to hydroxyl group in
Aer the preparation followed by adequate characterisation
cellulose decreases appreciably (Fig. 5a). Furthermore, IR of the prepared catalyst, we planned to initially explore it's
catalytic potential in click synthesis of 1,2,3-triazoles using
Table 2 Cell-CuI catalyzed click synthesis of 1,4-disubstituted-1,2,3-triazolesa
Entry
Halide (1)
Alkyne (2)
Product (4)
Time (h)
Yieldb (%)
TON
TOF
M.P. ꢁC Obs./(Lit)Ref
1
2
3
4
5
6
7
8
1a
1b
1c
1d
1e
1f
1g
1h
1i
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2b
2b
2b
2b
2b
2b
2c
2c
2c
2c
2c
2c
2c
2d
2d
2d
2d
2d
2e
2f
4aa
4ba
4ca
4da
4ea
4fa
4ga
4ha
4ia
2
4
4
3
4
5
5
5
6
6
3
4
4
4
4
4
4
4
4
4
4
5
5
3
4
4
4
4
4
3
4
3
3
4
4
96
89
91
89
87
88
94
85
82
81
89
88
92
89
93
87
86
85
90
87
84
87
83
85
90
89
85
96
80
85
85
95
87
84
85
2487
2355
2408
2355
2302
2328
2487
2249
2170
2143
2355
2328
2434
2355
2461
2302
2276
2249
2381
2302
2223
2302
2196
2249
2381
2355
2249
2545
2116
2249
2249
2513
2302
2222
2249
1243
588
602
785
575
465
497
450
361
357
785
582
608
588
615
575
568
562
595
575
555
460
439
749
595
585
562
635
529
749
562
837
767
555
562
127–130/(128–130)31b
142–145/(143–144)41d
128–130/(129–131)41a
104–107/(105–106)41b
133–135/(136–137)41e
79–81/(79–81)41c
150–155/(156–157)31b
99–102/(99)41a
66–68/(68–70)36b
75–77/(74–75)41a
142–146/(150)41f
140–143
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
1j
4ja
1a
1b
1c
1d
1e
1f
1a
1b
1c
1d
1f
1g
1h
1a
1b
1c
1d
1g
1a
1a
1b
1c
1d
1e
1f
4ab
4bb
4cb
4db
4eb
4
4ac
4bc
4cc
4dc
4fc
4gc
4hc
4ad
4bd
4cd
4dd
4gd
4ae
4af
140–144/(150–151)41g
118–120/(—)41g
132–135/(—)35a
115–118
110–113/(114–115)41h
115–117
102–104/(104–106)41i
105–108/(—)32a
107–110
156–159/(177–178)41j
117–120
105–108/(99–100)41k
108–111
101–104
118–122
128–132
63–66/(65)41l
177–179/(176–177)41e
175–176
2f
2f
2f
2f
4bf
4cf
4df
4ef
143–146
164–166
145–148/(149–150)41e
145–148
2f
4ff
a
Reaction conditions: benzyl bromide(1 mmol), alkyne(1 mmol) and sodium azide (1.1 mmol), Cell-CuI (3.5 mol%), water (3 mL), 70 ꢁC. b Yields
refer to pure isolated compounds.
42140 | RSC Adv., 2014, 4, 42137–42146
This journal is © The Royal Society of Chemistry 2014

View Article Online
Paper
RSC Advances
benzyl bromide, phenyl acetylene and sodium azide as model evaluation of the scope of the protocol, it was further observed
substrates (Scheme 1). that the protocol developed was also effective with structurally
To begin with, to a well stirred mixture of benzyl bromide (1 diverse alkynes viz. p-tolyl ethyne, 2-pyridyl ethyne, phenyl
mmol), phenyl acetylene (1 mmol) and sodium azide (1.1 mmol) propargyl thioether, 4-(prop-2-ynyloxy) benzaldehyde, and N-
was added Cell-CuI (200 mg; ꢂ0.07 mmol of CuI) as catalyst. propargyl phthalimide (2b–f). The reactions once again fur-
Stirring was continued at room temperature under solvent-free nished expected 1,2,3-triazoles in excellent yields as well as
condition. Timely analysis of the reaction mixture (TLC) did not purity (Table 2). Since the protocol developed proved to be of
indicate any appreciable progress of the reaction. So as to wide generality to furnish range of 1,2,3-triazoles in excellent
examine the effect of solvent, the model reaction was then yields as well as purity, we believed that, the protocol would be
carried out in different reaction media. However, the results of general use if scaled up. Accordingly, the model reaction
were not encouraging. Hence the model reactions were then between benzyl bromide, phenyl acetylene and sodium azide
carried out at the reux temperature of the selected reaction was carried out on 20 mmol scale when the reaction proceeded
medium and it was truly gratifying to notice that, the formation smoothly and furnished corresponding 1,2,3-triazole, 4aa, in
of desired 1-benzyl-4-phenyl-1H-1,2,3-triazole, 4aa, proceeds to 96% yield.
completion with the choice of water as an eco-benign reaction
In heterogeneously catalysed reactions reusability as well as
medium. Further optimisation of the reaction conditions with stability of the catalyst is of importance both from economical
respect to reaction temperature as well as catalyst loading and environmental point of view. Hence, aer completion of
revealed that, in aqueous medium desired triazole 4aa is gram scale model reaction, the catalyst was separated by
obtained in excellent yield at 70 ꢁC using 100 mg of Cell-CuI ltration, washed with ethyl acetate, acetone, dried in air and
(ꢂ0.035 mmol of CuI, 3.7 mol%) as the catalyst (Table 1). was used in next run. It was noticed that the recovered catalyst
Compared to benzyl bromide, benzyl chloride being less toxic, could be used for ve consecutive cycles without appreciable
less expensive and easier to handle, the model reaction was change in the yield of desired triazole (Fig. 6). From the stability
then carried out using benzyl chloride as the substrate. view point, we initially checked the leaching behaviour of the
However, the reaction required longer time and furnished a catalyst. Thus, aer separation of the catalyst, the resultant
mixture of products (TLC).
ltrate was analysed using AAS. The results were negative. In
Mechanism of copper catalysed synthesis of 1,2,3-triazoles substantiation of this observation, we also performed ICP-AES
has been the subject of exhaustive study and those have recently analysis of the recovered catalyst. During the analysis of the
been reviewed by Berg et al.40 They have emphasised on dinu- catalyst recovered aer h cycle, only 0.6% leaching of the
clear mechanism of CuAAC. Based upon their studies we catalyst was noticed. SEM images (Fig. 4c and d) of the reused
propose following mechanism for the formation of 1,2,3-tri- catalyst did not exhibit any morphological changes during
azoles (Scheme 2).
recycling of the catalyst.
The nano sized catalysts are claimed to offer the advantages
In recent years there being many reports on the development
of better yields, more reactivity as well as selectivity. In support of new catalysts for one-pot synthesis of 1,2,3-triazoles, lately we
of this claim, we planned to compare the catalytic efficiency of planned to compare the protocol developed by us with the
Cell-CuI NPs with commercially available CuI. Accordingly, two protocols reported recently for the same purpose. From the
model reactions were carried out under the established reaction results summarized in Table 3, we concluded that, each
conditions using Cell-CuI NPs (100 mg, 3.7 mol% CuI) and protocol has its own merits as well as demerits. However, from
commercially available CuI (7 mg, 3.7 mol%) as catalysts. Upon view point of cost, operational simplicity, ease of preparation of
completion of the reactions followed by routine work-up, the the catalyst, its easier separation from the reaction mixture and
expected triazole, 4aa, was obtained in 94% and 72% yield, avoidance of conventional purication, the protocol developed
respectively. The results clearly justify the choice of Cell-CuI NPs by us is superior and easily adaptable.
as the catalyst in one-pot synthesis of 1,2,3-triazoles (Table 1).
Next, we turned our attention to examine generality of the
reaction conditions. Accordingly benzyl bromide component in
the model reaction was replaced with 4-chloro, 4-uoro, 4-
methyl, 4-methoxy, 4-nitro as well as 2-chloro benzyl bromide
(1a–g). In each case, corresponding 1,2,3-triazole was obtained
in excellent yield (Table 2, entries 1–7) and most gratifyingly, the
resultant product did not require any further purication by
conventional methods. During the extension of the protocol
towards aliphatic bromides it was observed that, with the choice
of ethyl bromoacetate as an activated aliphatic bromide, the
reaction furnished desired triazole, 4ha, in acceptable yield
(Table 2, entry 8). However, in case of non-activated alkyl
halides like n-pentyl bromide as well as n-octyl bromide, the
reaction required longer reaction time and furnished corre-
sponding triazoles in lower yields (Table 2, entry 9, 10). During Fig. 6 Reusability of the Cell-CuI catalyst.
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 42137–42146 | 42141

View Article Online
RSC Advances
Paper
Table 3 Comparison of catalytic efficiency of Cell-CuI with other reported catalysts in synthesis of 4aa
No.
Catalyst (mol% mgꢀ1
)
Conditions
Time (h)
Yield (%)
Ref.
1
2
Cell-CuI NPs 100 mg
Cu–Al2O3 NPs, 10 mg
70 ꢁC, H2O
RT, H2O
2
3
96
92
This work
31a
3
4
5
6
7
8
9
10
11
12
13
14
Cu NPs on charcoal (1 mol%)
Cu NPs on activated carbon (0.5 mol%)
Zn/C, (10 mol%)
100 ꢁC, H2O
70 ꢁC, H2O
50 ꢁC, DMF
90 ꢁC, H2O
70 ꢁC, H2O
70 ꢁC, H2O
80 ꢁC, H2O
100 ꢁC, H2O
55 ꢁC, EtOH
70 ꢁC, H2O
100 ꢁC, H2O
80 ꢁC, H2O microwave
0.6
3
15
15
3
12
91
98
81
90
93
93
98
90
88
91
87
98, 98
31b
31c
41c
35b
32a
33a
35a
35c
33b
34a
36b
34b
CuI–Zeolite (CuI-USY),10 mol%
CuFe2O4 NPs, 5 mol%
Cu/SiO2 composite (10 mol%)
Silica immobilised NHC-Cu(I), 0.5 mol% Cu
P4VPy-CuI NPs (100 mg)
Cu2O nanocrystals (cube)
OSPs – CuBr, 2.5 mol%
g-Fe2O3/HAP NPs, 5 mol%
CuBr on graphene oxide/Fe3O4 (benzyl
chloride), 5 mol%
6
15a
7
4
5
8 h, 10a
15
16
Cu(II)/PBS/HMPO, 10 mg
Graphene-g-Fe2O3 magnetic nano–composite,
50 mg
100 ꢁC, H2O
3.5
NR
96
92
34c
36c
60 ꢁC, H2O, inert atmosphere
a
Time in minutes; NA: not reported.
Preparation of cellulose supported cuprous iodide (Cell-CuI)
catalyst
Conclusion
In summary, we have reported the preparation, characterisation
as well as use of cellulose supported CuI nanoparticles (Cell-CuI
NPs) as a new heterogeneous catalyst in click synthesis of 1,2,3-
triazoles. Use of water as an eco-benign reaction medium,
excellent yields, avoidance of conventional purication tech-
niques and reusability of the catalyst for ve consecutive runs
without appreciable change in composition as well as activity of
the catalyst make this green protocol a viable alternative for
one-pot synthesis of 1,4-disubstituted-1,2,3-triazoles.
To a stirred well suspension of CuI (0.190 g, 1 mmol) in meth-
anol (30 mL) was added microcrystalline cellulose (2 g) and
stirring was continued overnight. The reaction mixture was
ltered and residue was washed repeatedly with methanol and
nally with acetone. It was dried in air and then at 50 ꢁC for six
hours under vacuum. The resultant catalyst (Cell-CuI) was
characterised by XRD, HRTEM, SEM, ICP-AES, EDS, and FT-IR
techniques.
Representative procedure: synthesis of 1-benzyl-4-phenyl-1H-
1,2,3-triazole, 4aa
Experimental
General methods
Benzyl bromide (1 mmol), sodium azide (1.1 mmol) and phenyl
acetylene (1 mmol) were placed in a round bottom ask. Water
(2 mL) and cellulose-CuI (0.1 gm) were added and the reaction
Benzyl halides (Aldrich), alkynes (Aldrich/Alfa Aesar), sodium
azide (Sd Fine Chemicals, Mumbai), copper(I) iodide (Spec-
trochem, Mumbai) and microcrystalline cellulose (SRL, Mum-
bai) were used as received. All the melting points were recorded
using Kumar melting point apparatus. IR spectra were recorded
as neat using Thermo Scientic Nicolet iS10 FT-IR Spectrom-
eter. 1H NMR (300 MHz) and 13C NMR (75.4 MHz) spectra were
recorded using Bruker Avance-II spectrometer. High resolution
mass spectra (HRMS) were recorded using Thermo Scientic Q-
Exactive, Accela 1250 pump, instrument. X-Ray Powder
Diffraction (XRD) data were collected on X-Ray Powder
ꢁ
mixture was heated at 70 C. Aer completion of the reaction
(TLC), the reaction mixture was ltered and the lter was
washed with ethyl acetate (4 ꢃ 10 mL). The organic extract was
washed with water, brine and dried over Na2SO4. The removal of
solvent under vacuum furnished corresponding 1,2,3-triazole,
which did not require further purication. The recovered cata-
lyst was washed with acetone, dried in air and reused.
Gram-scale synthesis of 1-benzyl-4-phenyl-1H-1,2,3-triazole,
4aa
Diffractometer D2 PHASER, Bruker. Copper content in the Benzyl bromide (20 mmol), phenyl acetylene (20 mmol) and
supported catalyst was determined by inductively coupled sodium azide (22 mmol) were placed in 100 mL of round bottom
plasma atomic emission spectroscopy (ICP-AES) using ARCOS ask. Water (30 mL) and cellulose-CuI ꢁ(2 gm) were added and
ICP-AES. Scanning electron micrographs were obtained using the reaction mixture was heated at 70 C. Aer completion of
JSM-7600 F instrument. HRTEM were obtained using Trans- the reaction (TLC), the reaction mixture was ltered and washed
mission Electron Microscopy (TEM) micrographs, TECNAI F20 with ethyl acetate (4 ꢃ 20 mL). The collected organic extract was
Philips operated at 200 kV.
washed with water, brine and dried over Na2SO4. The solvent
42142 | RSC Adv., 2014, 4, 42137–42146
This journal is © The Royal Society of Chemistry 2014

View Article Online
Paper
RSC Advances
was removed under vacuum to give corresponding 1-benzyl-4- 1H); 13C NMR (75.4 MHz, CDCl3): d 51.65 (CH2), 120.43 (ArCH),
phenyl-1H-1,2,3-triazole, in excellent yield (96%) as well as 122.42 (ArCH), 122.96 (ArCH), 127.61 (ArCH), 130.02 (ArCH),
purity.
130.38 (ArCH), 130.58 (ArCH), 132.15 (ArC), 133.77 (ArC), 137.29
All the compounds were adequately characterised by phys- (ArCH), 148.22 (ArC), 148.98 (ArCH), 149.95 (ArC); HRMS: mass
ical as well as chemical methods. Spectral data of unknown calculated for [C14H11ClN4]: 271.0750 [M + H]+ and 293.0570 [M
compounds is summarised below. For original spectra of + Na]+; obs. mass: 271.0745 [M + H]+ and 293.0564 [M + Na]+.
unknown compounds please see ESI.†
2-(1-(4-Nitrobenzyl)-1H-1,2,3-triazol-4-yl)
pyridine,
4gc.
1-(4-Chlorobenzyl)-4-p-tolyl-1H-1,2,3-triazole, 4bb. Off-white Yellow solid; M.P.: 156–159 ꢁC; IR (neat): 2918, 2848, 2342, 1594,
solid; M.P.: 140–143 ꢁC; IR (neat): 2917, 2359, 1716, 1559, 1568, 1543, 1515, 1430, 1418, 1352, 1228, 1121, 1079, 995, 783
1489, 1340, 1219, 1089, 1048, 848, 754, 723 cmꢀ1; 1H NMR (300 cmꢀ1; H NMR (300 MHz, CDCl3): d 5.73 (s, 2H), 7.25–7.29 (m,
1
MHZ, CDCl3): d 2.38 (s, 3H), 5.55 (s, 2H), 7.23 (d, 2H, J ¼ 7.8 Hz), 1H), 7.48 (d, 2H, J ¼ 8.4 Hz), 7.79–7.84 (m, 1H), 8.17 (s, 1H),
7.27 (d, 2H, J ¼ 2.4 Hz), 7.35–7.38 (m, 2H), 7.38 (d, 2H, J ¼ 1.8 8.20–8.27 (m, 3H), 8.57 (d,1H J ¼ 4.8 Hz); 13C NMR (75.4 MHz,
Hz), 7.64 (s, 1H), 7.70 (d, 2H, J ¼ 8.4 Hz);13C NMR (75.4 MHz, CDCl3): d 53.35 (CH2), 120.62 (ArCH), 122.71 (ArCH), 123.29
CDCl3): d 21.27 (CH3), 53.47 (CH2), 119.09 (ArCH), 125.64 (ArCH), 124.38 (ArCH), 128.78 (ArCH), 137.73 (ArCH), 141.35
(ArCH), 127.48 (ArC), 129.36 (ArCH), 129.37(ArCH), 129.52 (ArC), 148.18 (ArC), 148.73 (ArCH), 149.37 (ArC), 156.28(ArC);
(ArCH), 133.22 (ArC), 134.84 (ArC), 138.19 (ArC), 148.36 (ArC); HRMS: mass calculated for [C14H11N5O2]: 282.0991 [M + H]+ and
HRMS: mass calculated for [C16H14ClN3]: 284.0955 [M + H]+ and 304.0810 [M + Na]+; obs. mass: 282.0986 [M + H]+ and 304.0805
306.0774 [M + Na]+; obs. mass: 284.0949 [M + H]+ and 306.0768 [M + Na]+.
[M + Na]+.
Ethyl 2-(4-(pyridin-2-yl)-1H-1 2 3-triazol-1-yl) acetate, 4hc.
1-(4-Methoxybenzyl)-4-p-tolyl-1H-1,2,3-triazole, 4eb. Yellow- Grey solid; M.P.: 117–120 ꢁC; IR (neat): 3165, 3042, 2969, 2345,
brown solid; M.P. 132–135 ꢁC; IR (neat): 3091, 2917, 1716, 1742, 1712, 1684, 1610, 1545, 1440, 1215 cmꢀ1; H NMR (300
1
1599, 1513, 1456, 1108, 1078, cmꢀ1; 1H NMR (300 MHz, CDCl3): MHz, CDCl3): d 1.32 (t, 3H, J ¼ 7.2 Hz), 4.30 (q, 2H, J ¼ 7.2 Hz),
d 2.37 (s, 3H), 3.82 (s, 3H), 5.51 (s, 2H), 6.93 (d, 2H, J ¼ 8.7 Hz), 5.24 (s, 2H), 7.28–7.30 (d,1H, J ¼ 9 Hz), 7.81–7.87 (t, 1H, J ¼ 7.8
7.21–7.29 (m, 4H), 7.60 (s, 1H),7.69 (d, 2H, J ¼ 8.1 Hz); 13C NMR Hz), 8.23 (d, 1H, J ¼ 7.8 Hz), 8.37 (s, 1H), 8.61 (d, 1H, J ¼ 4.5 Hz);
(75.4 MHz, CDCl3): d 21.27 (CH3), 53.79 (CH2), 55.35 (OCH3), 13C NMR (75.4 MHz, CDCl3): d 14.07 (CH3), 51.08 (CH2), 62.57
114.51 (ArCH), 118.97 (ArCH), 125.61 (ArCH), 126.65 (ArC), (CH2), 120.42 (ArCH), 122.99 (ArCH), 123.51 (ArCH), 137.05
127.69 (ArC), 129.50 (ArCH), 129.68 (ArCH), 137.99 (ArC), (ArCH), 148.69 (ArCH), 149.97 (ArC), 149.31 (ArC), 166 (C]O);
148.16(ArC), 159.95(ArC); HRMS: mass calculated for HRMS: mass calculated for [C11H12N4O2]: 233.1039 [M + H]+ and
[C17H17N3O]: 280.1450 [M + H]+ and 302.1269 [M + Na]+; obs. 255.0858 [M + Na]+; obs. mass: 233.1033 [M + H]+ and 255.0852
mass: 280.1444 [M + H]+ and 302.1264 [M + Na]+.
[M + Na]+.
1-(2-Chlorobenzyl)-4-p-tolyl-1H-1,2,3-triazole, 4. White
4-((1-(4-Chlorobenzyl)-1H-1, 2, 3-triazol-4-yl) methoxy) benzal-
solid; M.P.: 115–118 ꢁC; IR (neat): 2359, 1498, 1475, 1447, 1353, dehyde, 4bd. Off white solid; M.P.: 108–110 ꢁC; IR (neat): 3100,
1
1221, 1116, 1080, 1048, 836, 774, 752, 697 cmꢀ1; H NMR (300 2918, 1675, 1601, 1572, 1507, 1457, 1160, 1112, 772, 756 cmꢀ1
;
MHz, CDCl3): d 2.38 (S, 3H), 5.72 (s, 2H), 7.22 (s, 1H), 7.248 (s, 1H NMR (300 MHz, CDCl3): d 5.28 (s, 2H), 5.53 (s, 2H), 7.09 (d,
2H), 7.30–7,36 (m, 2H), 7.47 (m, 1H), 7.72 (d, 2H, J ¼ 8 Hz), 7.74 2H, J ¼ 8.4 Hz), 7.24 (d, 2H, J ¼ 8.4 Hz), 7.36 (d, 2H, J ¼ 8.4 Hz),
(s, 1H); 13C NMR (75.4 MHz, CDCl3): d 21.28(CH3), 51.41(CH2), 7.59 (s, 1H), 7.83 (d, 2H, J ¼ 8.7 Hz), 9.89 (s, 1H); 13C NMR (75.4
119.46 (ArCH), 125.64 (ArCH), 127.63(ArCH), 129.50 (ArCH), MHz, CDCl3): d 53.58 (CH2), 62.14 (CH2), 115.07 (ArCH), 122.77
129.91 (ArCH), 130.20(ArCH), 130.25 (ArCH), 132.61 (ArC), (ArCH), 129.41 (ArCH), 129.46 (ArCH), 130.40 (ArC), 131.99
133.42 (ArC), 138.08 (ArC), 148.23 (ArC); HRMS: mass calculated (ArCH), 132.80 (ArC), 135.01 (ArC) 143.84 (ArC), 163.08 (ArC),
for [C16H14ClN3]: 284.0955 [M + H]+ and 306.0774 [M + Na]+; obs. 190.75 (CHO); HRMS: mass calculated for [C17H14ClN3O2]:
mass: 284.0949 [M + H]+ and 306.0768 [M + Na]+.
328.0853 [M + H]+; obs. mass: 328.0847 [M + H]+.
2-(1-(4-Chlorobenzyl)-1H-1,2,3-triazol-4-yl) pyridine, 4bc.
4-((1-(4-Fluorobenzyl)-1H-1 2 3-triazol-4-yl)methyl) benzal-
Pale yellow solid; M.P.: 115–117 ꢁC; IR (neat): 2917, 2848, 2342, dehyde, 4cd. White solid; M.P.: 101–104 ꢁC; IR (neat): 3129,
1716, 1683, 1594, 1540, 1430, 1344, 1228, 1079, 995, 783, 765, 2844, 1683, 1603, 1540, 1457, 1231, 1222, 1131, 1110, 744 cmꢀ1
;
1
740 cmꢀ1; H NMR (300 MHz, CDCl3): d 5.58 (s, 2H), 7.25–7.39 1H NMR (300 MHz, CDCl3): d 5.27 (s, 2H), 5.52 (s, 2H), 7.09 (d,
(m, 5H), 7.80–7.86 (m, 1H), 8.17 (s, 1H), 8.22 (d, 1H, J ¼ 8.1 Hz), 4H, J ¼ 7.8), 7.29 (s, 2H), 7.57 (s, 1H), 7.83 (d, 2H, J ¼ 8.1 Hz),
8.56 (d, 1H, J ¼ 3.6 Hz); 13C NMR (75.4 MHz, CDCl3): d 3.67 9.89 (s, 1H, CHO); 13C NMR (75.4 MHz, CDCl3): d 53.57 (CH2),
(CH2), 120.61 (ArCH), 122.51 (ArCH), 123.12 (ArCH), 129.40 62.16 (CH2), 115.07 (ArCH), 116.07 (ArCH), 116.36 (ArCH),
(ArCH), 129.60 (ArCH), 132.81 (ArC), 134.98 (ArC), 137.83 122.70 (ArCH),129.99 (ArC), 130.10 (ArCH), 130.40 (ArC), 131.97
(ArCH), 147.89 (ArC), 148.85 (ArCH), 149.49 (ArC); HRMS: mass (ArC), 143.76 (ArC), 163.09 (ArC), 190.72 (CHO); HRMS: mass
calculated for [C14H11ClN4]: 271.0750 [M + H]+ and 293.0570 [M calculated for [C17H14FN3O2]: 312.1148 [M + H]+ and 334.0968
+ Na]+; obs. mass: 271.0745 [M + H]+ and 293.0564 [M + Na]+.
[M + Na]+; obs. mass: 312.1143 [M + H]+ and 334.0962 [M + Na]+.
2-(1-(2-Chlorobenzyl)-1H-1,2,3-triazol-4-yl) pyridine, 4fc. Pale
4-((1-(4-Methylbenzyl)-1H-1,2,3-triazol-4-yl)methyl) benzal-
yellow solid; M.P.: 107–110 ꢁC; IR (neat): 3160, 3050, 1716, 1680, dehyde, 4dd. Off white solid; M.P.: 118–122 ꢁC; IR (neat): 3145,
1
1604, 1434, 1355, 1226, 1193, 1088, 1072, 994 cmꢀ1; H NMR 3095, 2890, 1693, 1643, 1623, 1555, 1465, 1248, 1200, 745 cmꢀ1
;
(300 MHz, CDCl3): d 5.73 (s, 2H), 7.21–7.35 (m, 4H), 7.44 (d, 1H, 1H NMR (300 MHz, CDCl3): d 2.36 (s, 3H), 5.26 (s, 2H), 5.50 (s,
J ¼ 7.5 Hz), 7.76–7.82 (m, 1H), 8.19 (s, 1H), 8.21 (m, 1H), 8.56 (m, 2H), 7.09 (d, 2H, J ¼ 8.7 Hz), 7.20 (s, 4H), 7.55 (s, 1H), 7.83 (d,
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 42137–42146 | 42143

View Article Online
RSC Advances
Paper
2H, J ¼ 8.7 Hz), 9.88 (s, 1H); 13C NMR (75.4 MHz, CDCl3): d 21.16 CDCl3): d 33.43 (CH2), 51.37 (CH2), 122.99 (ArCH), 123.42 (ArCH)
(CH3) 54.15 (CH2), 62.18 (CH2), 115.08 (ArCH), 122.73 (ArCH), 127.57 (ArCH), 129.88 (ArCH), 130.18 (ArCH) 130.29 (ArCH),
128.22 (ArCH), 129.85 (ArCH), 130.33 (ArC), 131.25 (ArC), 131.98 131.98 (ArC), 132.48 (ArC), 133.48 (ArC), 134.04 (ArCH) 143.53
(ArCH), 138.90 (ArC), 143.51 (ArC), 163.15 (ArC), 190.78 (CHO); (ArC), 164.52 (C]O); HRMS: mass calculated for [C18H13ClN4O2]:
HRMS: mass calculated for [C18H17N3O2]: 308.1399 [M + H]+ and 353.0805 [M + H]+ and 375.0625 [M + Na]+; obs. mass: 353.0800 [M
330.1218 [M + Na]+; obs. mass: 308.1394 [M + H]+ and 330.1213 + H]+ and 375.0619 [M + Na]+.
[M + Na]+.
4-((1-(4-Nitrobenzyl)-1H-1,2,3-triazol-4-yl) methoxy) benzal-
dehyde, 4gd. Yellow solid; M.P.: 128–132 ꢁC; IR (neat): 2917,
Acknowledgements
2849, 1703, 1684, 1653, 1600, 1540, 1472, 1457, 1345, 1128, Authors (UVD and PVC) thank University Grants Commission
1108, 755 cmꢀ1; 1H NMR (300 MHz, CDCl3): d 5.30 (s, 2H), 5.69 (UGC), New Delhi, India for nancial assistance and for the
(s, 2H), 7.10 (d, 2H, J ¼ 8.7 Hz), 7.43 (d, 2H, J ¼ 8.4 Hz), 7.68 (S, award of teacher fellowship, respectively. We gratefully
1H), 7.84 (d, 2H, J ¼ 8.7 Hz), 8.23 (d, 2H, J ¼ 8.7 Hz), 9.89 (s, 1H); acknowledge Dr A. S. Burungale, Principal, Yashavantrao Cha-
13C NMR (75.4 MHz, CDCl3): d 53.26 (CH2), 62.08 (CH2), 115.04 van Institute of Science, Satara, for encouragement.
(ArCH), 123.09 (ArCH), 124.37 (ArCH), 128.68 (ArCH), 130.46
(ArC), 132.01 (ArCH), 141.33 (ArC), 144.23 (ArC), 148.16 (ArC),
References
162. 99 (ArC), 190.74 (CHO); HRMS: mass calculated for
[C17H14N4O4]: 339.1093 [M + H]+ and 361.0913 [M + Na]+; obs.
mass: 339.1088 [M + H]+ and 361.0907 [M + Na]+.
1 For recent reviews and monographs, see (a) R. A. Sheldon,
I. Arends and U. Hanefeld, Green Chemistry and Catalysis,
Wiely-VCH, Weinheim, 2007; (b) A. J. Wangelin,
H. Neumann, D. Gordes, S. Klaus, D. Strubing and
M. Beller, Chem.–Eur. J., 2003, 9, 4286–4294; (c) P. Anastas
and N. Eghboli, Chem. Soc. Rev., 2010, 93, 301–312; (d)
2-((1-(4-Chlorobenzyl)-1H-1,2,3-triazol-4-yl) methyl)isoindoline-
1,3-dione, 4bf. White solid; M. P.: 174–176 ꢁC; IR (neat): 2918,
2849, 1771, 1709, 1653, 1466, 1436, 1104, 777, 755, 711 cmꢀ1; 1H
NMR (300 MHz, CDCl3): d 4.99 (s, 2H), 5.46 (s, 2H), 7.21 (d, 2H, J ¼
8.4 Hz), 7.35 (d, 2H, J ¼ 8.4 Hz), 7.53 (s, 1H), 7.73 (m, 2H), 7.86 (m,
2H); 13C NMR (75.4 MHz, CDCl3): d 33.04 (CH2), 53.44 (CH2),
122.66 (ArCH), 123.47 (ArCH), 129.34 (ArCH), 129.44 (ArCH),
132.02 (ArC), 132.93 (ArC), 134.11 (ArCH), 134.85 (ArC), 143.35
(ArC), 167.64 (C]O); HRMS: mass calculated for [C18H13ClN4O2]:
353.0805 [M + H]+ and 375.0625 [M + Na]+; obs. mass: 353.0800 [M
+ H]+ and 375.0619 [M + Na]+.
¨
¨
´
M. B. Gawande, V. D. B. Bonifacio, R. Luque, P. S. Branco
and R. S. Varma, Chem. Soc. Rev., 2013, 42, 5522–5551.
2 (a) L. Yin and J. Liebscher, Chem. Rev., 2007, 107, 133–173; (b)
L. L. Chng, N. Erathodiyil and J. Y. Ying, Acc. Chem. Res.,
2013, 46, 1825–1837.
3 (a) J. F. Billing and U. J. Nilsson, J. Org. Chem., 2005, 70,
4847–4850; (b) K. D. Bodine, D. Y. Gin and M. S. Gin, Org.
Lett., 2005, 7, 4479–4482; (c) F. Fazio, M. C. Bryan, O. Blixt,
J. C. Paulson and C. Wong, J. Am. Chem. Soc., 2002, 124,
14397–14402.
2-((1-(4-Fluorobenzyl)-1H-1,2,3-triazol-4-yl) methyl)isoindoline-
ꢁ
1,3-dione, 4cf. Off white solid; M.P.: 143–146 C; IR (neat): 3140,
2850, 1765, 1643, 1593, 1550, 1448, 1235, 1200, 1140, 750, 708
cmꢀ1; 1H NMR (300 MHz, CDCl3): d 4.97 (s, 2H), 5.46 (s, 2H), 7.05
(t, 2H, J ¼ 8.7 Hz), 7.26 (dd, 2H, J ¼ 4.5 & 5.1 Hz), 7.52 (S, 1H), 7.72
(m, 2H), 7.85 (m, 2H); 13C NMR (75.4 MHz, CDCl3): d 33.04 (CH2),
53.43 (CH2), 115.97 (ArCH), 116.26 (ArCH), 122.61 (ArC), 123.44
(ArCH), 129.94 (ArCH), 130.05 (ArC), 130.29 (ArC),132.03 (ArC),
134.09 (ArCH), 167.63 (C]O); HRMS: mass calculated for
[C18H13FN4O2]: 337.1101 [M + H]+ and 359.0920 [M + Na]+; obs.
mass: 337.1095 [M + H]+ and 359.0915 [M + Na]+.
¨
4 S. Lober, P. Raodriguez-Loaiza and P. Geminer, Org. Lett.,
2003, 5, 1753–1755.
5 (a) J. K. Lee, Y. S. Chi and L. S. Choi, Langmuir, 2004, 20,
3844–3847; (b) J. P. Collman, N. K. Devaraj and
C. E. D. Chidsey, Langmuir, 2004, 20, 1051–1053; (c)
H. R. Rengifo, L. Chen, C. Grigoras, J. Ju and
J. T. Koberstein, Langmuir, 2008, 24, 7450–7456.
6 (a) M. J. Genin, D. A. Allwine, D. J. Anderson,
M. R. Barbachyn, D. E. Emmert, S. A. Garmon,
D. R. Graber, K. C. Grega, J. B. Hester, D. K. Hutchinson,
J. Morris, R. J. Reischer, C. W. Ford, G. E. Zurenko,
J. C. Hamel, R. D. Schaadt, D. Stapert and B. H. Yagi, J.
Med. Chem., 2000, 43, 953–970; (b) D. R. Buckel,
C. J. M. Rockell, H. Smith and B. A. Spicer, J. Med. Chem.,
1986, 29, 2262–2267.
7 T. Lee, M. Cho, S. Y. Ko, H. J. Youn, D. J. Baek, W. J. Cho,
C. Y. Kang and S. Kim, J. Med. Chem., 2007, 50, 585–589.
8 (a) Y. Xia, Z. Fan, J. Yao, Q. Liao, W. Li, F. Qu and L. Peng,
Bioorg. Med. Chem. Lett., 2006, 16, 2693–2698; (b)
Y.-C. Duan, Y.-C. Ma, E. Zhang, X.-J. Shi, M.-M. Wang,
X.-W. Ye and H.-M. Liu, Eur. J. Med. Chem., 2013, 62, 11–19.
9 (a) S. Palhagen, R. Canger, O. Henriksen, J. A. Van Parys,
M. E. Riviere and M. A. Karolchyk, Epilepsy Res., 2001, 43,
115–124; (b) R. Alvarez, S. Velazquez, A. San-Felix,
2-((1-(4-Methylphenyl methyl)-1H-1,2,3-triazol-4-yl) methyl)-
ꢁ
isoindoline-1,3-dione, 4df. Yellow solid; M. P.: 164–166 C; IR
(neat): 3123, 1771, 1713, 1613, 1462, 1425, 1131, 1115, 771, 708
1
cmꢀ1; H NMR (300 MHz, CDCl3): d 2.35 (s, 3H), 4.97 (s, 2H),
5.44 (s, 2H), 7.17 (s, 4H), 7.49 (s, 1H), 7.72 (m, 2H), 7.85 (m, 2H);
13C NMR (75.4 MHz, CDCl3): d 21.15 (CH3), 33.08 (CH2), 54.01
(CH2), 122.53 (ArCH), 123.44 (ArCH), 128.16 (ArCH), 129.77
(ArCH), 131.39 (ArC), 132.05 (ArC), 134.06 (ArCH), 138.71 (ArC),
143.08 (Ar–C), 167.65 (C]O); HRMS: mass calculated for
+
[C19H16N4O2]: 333.1352 [M + H]+ and 355.1171 [M + Na] ; obs.
mass: 333.1346 [M + H]+ and 355.1165 [M + Na]+.
2-((1-(2-Chlorobenzyl)-1H-1 2 3-triazol-4-yl)methyl)isoindoline-
1,3-dione, 4ff. Pale yellow solid; M.P.: 145–148 ꢁC; IR (neat): 3035,
2948, 1769, 1690, 1600, 1450, 1435, 1145, 1115, 765, 740 cmꢀ1; 1H
NMR (300 MHz, CDCl3): d 4.99 (s, 2H), 5.63 (s, 2H), 7.15–7.44 (m,
4H), 7.62 (s, 1H), 7.72 (m, 2H), 7.85 (m, 2H); 13C NMR (75.4 MHz,
42144 | RSC Adv., 2014, 4, 42137–42146
This journal is © The Royal Society of Chemistry 2014

View Article Online
Paper
RSC Advances
S. Aquaro, E. D. Clercq, C.-F. Perno, A. Karlsson, J. Balzarini 25 A. Kumar, S. Aerry, A. Saxena, A. De and S. Mozumdar, Green
and M. J. Camarasa, J. Med. Chem., 1994, 37, 4185–4194. Chem., 2012, 14, 1298–1301.
10 (a) B. R. Buckle, D. J. Outred, C. J. M. Rockell, H. Smith and 26 M. Chtchigrovisky, A. Primo, P. Gonzalez, K. Molviger,
B. A. Spicer, J. Med. Chem., 1983, 26, 251–254; (b)
S. A. Bakunov, S. M. Bakunova, T. Wenzler, M. Ghebru,
M. Robitzer, F. Quignard and F. Taran, Angew. Chem., Int.
Ed., 2009, 48, 5916–5920.
K. A. Werbovetz, R. Brun and R. R. Tidwell, J. Med. Chem., 27 R. B. Nasir Baig and R. S. Varma, Green Chem., 2013, 15,
2010, 53, 254–272. 1839–1843.
11 (a) H. Dehne, in Methoden der Organischen Chemie (Houben- 28 (a) P. Appukkuttan, W. Dehaen, V. Fokin and E. V. D. Eycken,
Weyl), ed. E. Schumann, Thieme, Stuttgart, 1994, vol. E8d,
pp. 305–405; (b) W.-Q. Fan and A. R. Katritzky, in
Org. Lett., 2004, 6, 4223–4225; (b) A. Feldman, B. Colasson
and V. V. Fokin, Org. Lett., 2004, 6, 3897–3899.
Comprehensive Heterocyclic Chemistry II, ed. A. R. Katritzky, 29 (a) C. O. Kappe and E. V. D. Eycken, Chem. Soc. Rev., 2010, 39,
C. W. Rees and E. F. V. Scriven, Elsevier Science, Oxford,
1996, vol. 4, pp. 1–126.
1280–1290; (b) X. Xiong and L. Cai, Catal. Sci. Technol., 2013,
3, 1301–1307.
12 (a) G. L'abbe, Chem. Rev., 1969, 69, 345–363; (b) R. Huisgen, 30 For recent Review see: (a) B. Bervaux and F. E. Du Parez,
in 1,3-Dipolar Cycloaddition Chemistry, ed. A. Padwa, Wiley,
New York, 1984, ch. 1, pp. 1–176; (c) A. Padwa, in
Chem. Sci., 2012, 3, 959–966; (b) T. Jin, M. Yan and
Y. Yamamoto, ChemCatChem, 2012, 4, 1217–1229.
Comprehensive Organic Synthesis, ed. B. M. Trost and I. 31 (a) M. L. Kantam, V. S. Jaya, B. Sreedhar, M. M. Rao and
Fleming, Pergamon, Oxford, 1991, vol. 4, pp. 1069–1109;
(d) K. V. Gothelf and K. A. Jørgensen, Chem. Rev., 1998, 98,
863–909.
B. M. Choudary, J. Mol. Catal. A: Chem., 2006, 256, 273–
277; (b) H. Sharghi, R. Khalifeh and M. M. Doroodmand,
Adv. Synth. Catal., 2009, 351, 207–218; (c) F. Alonso,
Y. Moglie, G. Radivoy and M. Yus, Adv. Synth. Catal., 2010,
352, 3208–3214; (d) F. Alonso, Y. Moglie, G. Radivoy and
M. Yus, Org. Biomol. Chem., 2011, 9, 6385–6395.
13 For reviews on 1,3-dipolar cycloadditions please see: (a)
C. K. Sha and A. K. Mohanakrishan, in Synthetic
Applications of 1,3-Dipolar Cycloaddition Chemistry Toward
Heterocycles and Natural Products, ed. A. Padwa and W. H. 32 (a) B. S. P. Anilkumar, K. H. V. Reddy, B. Madhav, K. Ramesh
Pearson, Wiley, New York, 2003, pp. 623–680; (b)
S. Karlsson and H. E. Hogberg, Org. Prep. Proced. Int., 2001,
33, 103–172.
and Y. V. D. Nageswar, Tetrahedron Lett., 2012, 53, 4595–
4599; (b) N. Salam, A. Sinha, P. Mondal, A. S. Roy,
N. R. Jana and S. M. Islam, RSC Adv., 2013, 3, 18087–18098.
14 (a) H. C. Kolb, M. G. Finn and K. B. Sharpless, Angew. Chem., 33 (a) C. S. Radatz, L. D. A. Soares, E. R. Vieira, D. Alves,
Int. Ed., 2001, 40, 2004–2021; (b) C. W. Tornoe,
C. Christensen and M. Meldal, J. Org. Chem., 2002, 67,
3057–3062.
D. Russowsky and P. H. Schneider, New J. Chem., 2014, 38,
1410–1417; (b) K. Chanda, S. Rej and M. H. Huang, Chem.–
Eur. J., 2013, 19, 16036–16043.
15 V. V. Rostovtsev, L. G. Green, V. V. Fokin and K. B. Sharpless, 34 (a) X. Xiong, L. Cai, Y. Jiang and Q. Han, ACS Sustainable
Angew. Chem., Int. Ed., 2002, 41, 2596–2599.
16 F. Himo, T. Lovell, R. Hilgraf, V. V. Rosrovtsev,
L. Noodleman, K. B. Sharpless and V. V. Fokin, J. Am.
Chem. Soc., 2005, 127, 210–216.
Chem. Eng., 2014, 2, 765–771; (b) X. Xiong, H. Chen,
Z. Tang and Y. Jiang, RSC Adv., 2014, 4, 9830–9837; (c)
A. N. Prasad, B. M. Reddy, E.-Y. Jeong and S.-E. Park, RSC.
Adv., 2014, 4, 29772–29781.
17 (a) B. H. Lipshutz and B. R. Ta, Angew. Chem., Int. Ed., 2006, 35 (a) L. Wan and C. Cai, Catal. Lett., 2012, 142, 1134–1140; (b)
´ ´
45, 8235–8238; (b) C. T. Lee, S. Huang and B. H. Lipshutz,
Adv. Synth. Catal., 2009, 351, 3139–3142.
18 (a) S. Chassaing, A. S. S. Sido, A. Alix, M. Kumarraja, P. Pale
and J. Sommer, Chem.–Eur. J., 2008, 14, 6713–6721; (b)
V. Beneteau, A. Olmos, T. Boningari, J. Sommer and P. Pale,
Tetrahedron Lett., 2010, 51, 3673–3677; (c) J. Albadi,
M. Keshavarz, M. Abedini and M. Vafaie-nezhad, Chin.
Chem. Lett., 2012, 23, 797–800.
S. Chasseing, A. Alix, T. Boningari, K. S. S. Sido, M. Keller, 36 (a) M. Nasr-Esfahani, I. Mohammadpoor-Baltork,
P. Kuhn, B. Louis, J. Sommer and P. Pale, Synthesis, 2010,
1557–1567.
19 I. Jlalia, H. Elamar, F. Meganem, J. Herscovici and C. Girard,
Tetrahedron Lett., 2008, 49, 6756–6758.
20 P. Li, L. Wang and Y. Zhang, Tetrahedron, 2008, 64, 10825–
10830.
21 U. Sirion, Y. J. Bae, B. S. Lee and D. Y. Chi, Synlett, 2008,
2326–2330.
22 J. Albadi, M. Keshavarz, F. Shirini and M. Vafaie-nezhad,
Catal. Commun., 2012, 27, 17–20.
A. R. Khosropour, M. Moghadam, V. Mirkhani,
S. Tangestaninejad and H. A. Rudbari, J. Org. Chem., 2014,
79, 1437–1443; (b) S. R. Kale, S. S. Kahandal,
M. B. Gawandeb and R. V. Jayaram, RSC Adv., 2013, 3,
8184–8192.
37 (a) S. D. Mitragotri, D. M. Pore, U. V. Desai and
P. P. Wadgaonkar, Catal. Commun., 2008, 9, 1822–1826 and
references therein; (b) M. A. Kulkarni, V. R. Pandurangi,
U. V. Desai and P. P. Wadgaonkar, C. R. Chim., 2012, 15,
745–752; (c) M. A. Kulkarni, U. P. Lad, U. V. Desai,
S. D. Mitragotri and P. P. Wadgaonkar, C. R. Chim., 2013,
16, 148–152; (d) M. A. Kulkarni, K. S. Pandit, U. P. Lad,
U. V. Desai and P. P. Wadgaonkar, C. R. Chim., 2013, 16,
689–695.
23 P. K. Khanna, R. Gokhale and V. V. V. S. Subbarao, J. Mater.
Sci., 2004, 39, 3773–3776.
24 B. Kaboudin, R. Mostafalu and T. Yokomatsu, Green Chem.,
2013, 15, 2266–2274.
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 42137–42146 | 42145

View Article Online
RSC Advances
Paper
38 Y. Xu, L. Zhang and Y. Cui, J. Appl. Polym. Sci., 2008, 110,
2996–3000.
39 K. Rajender Reddy and N. S. Kumar, Synlett, 2006, 14, 2246–
2250.
40 R. Berg and B. F. Straub, Beilstein J. Org. Chem., 2013, 9,
2715–2750.
41 (a) L. S. Campbell-Verduyn, L. Mirfeizi, R. A. Dierckx,
P. H. Elsinga and B. L. Feringa, Chem. Commun., 2009, 16,
Synlett, 2008, 15, 2326–2330; (f) Z. Gonda and Z. Novak,
Dalton Trans., 2010, 39, 726–729; (g) B. R. Buckley,
S. E. Dann, D. P. Harris, H. Heaney and E. C. Stubbs,
Chem. Commun., 2010, 46, 2274–2276; (h) D. Wang, N. Li,
M. Zhao, W. Shi, C. Ma and B. Chen, Green Chem., 2010,
12, 2120–2123; (i) Y. Kitamura, K. Taniguchi, T. Maegawa,
Y. Monguchi, Y. Kitade and H. Sajiki, Heterocycles, 2009,
77, 521–532; (j) T. Y. Kim, A. B. S. Elliott, K. J. Shaffer,
C. J. McAdam, K. C. Gordon and J. D. Crowley, Polyhedron,
2013, 52, 1391–1398; (k) R. Kumar, J. Arora, A. K. Prasad,
N. Islam and A. K. Verma, Med. Chem. Res., 2013, 22, 5624–
5631; (l) F. Saleem, G. K. Rao, A. Kumar, G. Mukherjee and
A. K. Singh, Organometallics, 2013, 32, 3595–3603.
´
´
´
2139–2141; (b) J. Gonzalez, V. M. Perez, D. O. Jimenez,
˜
G. Lopez-Valdez, D. Corona and E. Cuevas-Yanez,
Tetrahedron Lett., 2011, 52, 3514–3517; (c) X. Meng, X. Xu,
T. Gao and B. Chen, Eur. J. Org. Chem., 2010, 5409–5414;
(d) Z.-X. Wang and Z.-G. Zhao, J. Heterocycl. Chem., 2007,
44, 89–92; (e) U. Sirion, Y. J. Bae, B. S. Lee and D. Y. Chi,
42146 | RSC Adv., 2014, 4, 42137–42146
This journal is © The Royal Society of Chemistry 2014