On Water Cu@g-C3N4 Catalyzed Synthesis of NH-1,2,3-Triazoles via [2+3] Cycloadditions of Nitroolefins/Alkynes and Sodium Azide

Article abstract of DOI:10.1002/cctc.201801524

Here, we have reported fabrication of graphitic polymeric C₃N₄ supported CuCl₂ (Cu@g-C₃N₄) and characterized by powder X-ray diffraction, field emission scanning electron microscopy, high resolution transmission electron microscopy, X-ray photoelectron spectroscopy studies. An efficient and regioselective protocol for the on water synthesis of 4-aryl-NH-1,2,3-triazole derivatives via 1,3-diipolar cycloaddition reactions of nitroolefins/phenylacetylenes to sodium azide were demonstrated by using Cu@g-C₃N₄ as robust and reusable catalyst.

Full text of DOI:10.1002/cctc.201801524

Accepted Article
Title: On Water Cu@g-C3N4 Catalyzed Synthesis of NH-1,2,3-
Triazoles Via [2+3] Cycloadditions of Nitroolefins/Alkynes and
Sodium Azide
Authors: Subhash Banerjee, Soumen Payra, and Arijit Saha
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On Water Cu@g-C3N4 Catalyzed Synthesis of NH-1,2,3-Triazoles
Via [2+3] Cycloadditions of Nitroolefins/Alkynes and Sodium
Azide
Dr. Soumen Payra,[a] Dr. Arijit Saha[a] and Dr. Subhash Banerjee*,[a]
Abstract: Here, we have reported fabrication of graphitic polymeric
C3N4 supported CuCl2 (Cu@g-C3N4) and characterized by powder X-
ray diffraction, field emission scanning electron microscopy, high
resolution transmission electron microscopy, X-ray photoelectron
spectroscopy studies. An efficient and regioselective protocol for the
on water synthesis of 4-aryl-NH-1,2,3-triazole derivatives via 1,3-
diipolar cycloaddition reactions of nitroolefins/phenylacetylenes to
sodium azide were demonstrated by using Cu@g-C3N4 as robust
and reusable catalyst.
Development of sustainable protocols for the synthesis of 1,2,3-
triazole scaffolds have emerged one of the thrust area of
research for organic chemist due to their exclusive
pharmaceutical [1-6], agrochemical [7], medicinal [8-13] and
many other applications [14-21]. Several strategies have been
reported for the synthesis of 1,2,3-triazoles [22-32] and
Huisgen’s dipolar cycloaddition of organic azides and alkynesis
the most straightforward route [33] Subsequently, transition
metal catalyzed alkyne-azide cycloaddition (MAAC; M = Cu [34-
Figure 1. Some bioactive molecules containing NH-1,2,3-triazole unit.
38]/Ag [39-40]/Ru [41-43]/Ir [44-45]/Al [46]) have been
developed for the synthesis of 1,4 or 1,5-disubstitutedor 1,4,5-
Most of the above protocols for the preparation of NH-1,2,3-
triazoles have their own advantages. However, the
trisubstituted triazoles [34-46]. Among these, CuAAC perhaps is
practical/industrial use of those protocol were limited by low
most powerful method which mostly produce 1,4-disubstituted-
yields, potential substrate polymerization (cyclotrimerization),
1,2,3-triazoles. Again, NH-1,2,3-triazole is one of the important
use of environmentally polluting heavy-metal ions which cannot
class of 1,2,3-triazoles with numerous applications. Particularly,
be regenerated/reused [72]. Heterogenization of the existing
these moieties can further be modified synthetically with
homogeneous catalysts could be an attractive solution to
alkyl/aryl/acyl-functionality with choice to yield N2-substituted
circumvent these problems. The design of heterogeneous
1,2,3-triazoles [47-49]. Few pharmaceutically active drugs
catalysts has to take into account of high efficiencies,
containing NH-1,2,3-triazole scaffold were shown in Figure 1
selectivities, stability and most essentially environmental
acceptability.
[50-54].
However, the synthesis of NH-1,2,3-triazoles is fairly challenging
compared to the direct synthesis of substituted triazoles [55-61].
Very recently, graphitic carbon nitride (g-C3N4) material has
being emerged as an appealing and fascinating material, and
NH-1,2,3-triazoles were prepared by the CAAC reaction of
attracted a great deal of attention in a wide community [72–78].
alkyne and TMSN3 followed by deprotection of the TMS [55,59],
The unique features of C3N4 are that highest thermal and
Pd-catalyzed reactions of alkenyl bromides and sodium azide
chemical stability, abundant nitrogen functionalities on the
[60], or via multicomponent reactions [62-66], or through alkynes
surface sites acts as strong Lewis base sites, while the -
with NaN3 in DMSO [67]. It is noteworthy, that the condensation
bonded planar layered configurations are utilized to anchor
of nitroalkanes and NaN3 is a popular method for the synthesis
desired metal which allows its direct use as heterogeneous
of NH-1,2,3-triazoles or N1 substituted triazoles. Such type of
catalysts [72]. Pristine g-C3N4 used for Friedel–Crafts reaction
[73], oxidation of benzene to phenol [79], cycloaddition of CO2 to
propylene oxide to propylene carbonate [80]. Few g-C3N4
composites have also been developed. For example, Fe-g-C3N4
condensation has been carried out by using p-TsOH/DMF [68],
Amberlyst-15/DMF [69], acetic acid/flow chemistry [70],
Bi2WO6/water [71], Ce(OTf)3 [24], Cu(OTf)2 [30].
has been developed for degradation of methylene blue, water
splitting [81], photo oxidation of benzene to phenol [82-83] and
decomposition of nitric oxide [84]. BiVO4-g-C3N4 nanocomposites
was used for oxidation of alcohol/amines, VO-g-C3N4 was
employed for the oxidative esterification of alcohols [78],
graphene/C3N4 composites have used for visible-light
[a] Dr. S. Payra, Dr. A. Saha, Dr. S. Banerjee
Department of Chemistry,
Guru Ghasidas Vishwavidyalaya
Bilaspur, C.G., India, 495009
Tel: +91-7587401979
photocatalytic
H2-production
[85],
g-C3N4/N-doped
Fax: +91 7752 260148
E-mail: ocsb2009@gmail.com
graphene/NiFe-layered double hydroxide used for solar-driven
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10.1002/cctc.201801524
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photoelectrochemical water oxidation [86], Pd-g-C3N4 was
developed for Sonogashira reactions [72]. However, to the best
of our knowledge, g-C3N4 supported copper chloride (Cu@g-
C3N4) material has not been reported in the literature. As a part
of continuous interest in the development of heterogeneous
synthetic methodologies using nanomaterials [87-92], here, we
have developed Cu@g-C3N4 for the [3+2]cycloaddition of
nitroolefins/alkynes with sodium azide leading to NH-1,2,3-
triazoles (Scheme 1).
weaker one at 2 13.1o is related to in-plane tris-s-triazine
structural packing. Thus, the interlayer stacking and in plane
packing were remained intact after the immobilization of Cu on
C3N4 polymer. However, no additional peak corresponding to Cu
was observed in the powder XRD pattern of Cu@g-C3N4. This
could probably be due to the high dispersion of CuCl2 in the
support [78]. The field emission scanning electron microscopy
(FE-SEM) studies of g-C3N4 (Figure 3a) and Cu@g-C3N4 (Figure
3b) have clearly demonstrated that the morphology of g-C3N4
remained intact after the immobilization of Cu.
Scheme 1. Fabrication of Cu@g-C3N4 for the synthesis of 4-aryl-NH-1,2,3-
triazoles from -nitrostyrenes/phenylacetylens.
At the outset, we have prepared the catalyst simply by the
calcination of urea followed by immobilization of CuCl2 under
sonication. The reaction mixture was then centrifuged, washed
with ethanol and dried up at 60 oC under vacuum for 16 h to
provide CuCl2@g-C3N4 as off-white bluish solid (Scheme 1). The
as prepared material was characterized by using analytical
techniques. Figure 2 represents the powder X-ray diffraction
(XRD) of g-C3N4 (black line) and CuCl2@g-C3N4 (red line).
3000
Powder XRD pattern of CuCl2@g-C N
3
4
Figure 3. FE-SEM images of (a) g-C3N4 and (b) Cu@g-C3N4; EDAX pattern of
Powder XRD pattern of g-C N
3
4
2500
2000
1500
1000
500
(c) g-C3N4 and (d) Cu@g-C3N4.
28.1
(002)
13.3
18.1
0
10
20
30
40
50
60
2 
Figure 2. Powder XRD pattern of g-C3N4 and Cu@g-C3N4.
On the other hand, the EDAX spectrum of Cu@C3N4 (Figure 3d)
confirms the presence of carbon, nitrogen, copper and chlorine
in the sample. This suggested that the CuCl2 remained stable
during immobilization process on the surface of C3N4. On the
other hand, as expected only peaks for elemental carbon and
nitrogen were observed in the EDAX spectrum of pure g-C3N4
and no peak for CuCl2 was observed (Figure 3c). As seen in
Figure 2 both the material showed a broad peak at 2 28.1o
which suggested the presence graphite-like interlayer stacking
of the aromatic systems in C3N4 (JCPDS 87-1526) [78]. The
Figure 4. (a) HR-TEM image of Cu@g-C3N4; (b) SAED pattern of Cu@g-C3N4;
(c-d) magnified HR-TEM images of Cu@g-C3N4.
.
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The high resolution transmission electron microscopy images of g-
Cu@g-C3N4 have been presented in Figure 4. As seen from the
Figure 4a, Cu@g-C3N4 exhibits a sheet-like structure similar to that
of g-C3N4 with different thickness.
The peaks allocated at 402.8 and 404.6 eV are due to amino
functionalized hydrogen (C-N-H) and effects of charge densities
[94]. In the XPS spectra of Cu2+ 2p (Figure 5c) four distinguished
peaks were observed.
The resilient peaks at 930.1 eV and 950.2 eV are due to the two
types of Cu species, which corresponds to the strong spin-orbit
coupling of Cu 2p3/2 and Cu 2p1/2 [95]. The other two peaks at
940.7 eV and 970 eV in lower intensity is might be due to Cu-N
and Cu-C bond formation in the surface of the catalyst. Figure
5d demonstrated the XPS spectra of Cl (Figure 5d) two stronger
peaks were determined at 198.1 eV and 199.8 eV is mainly due
to the strong spin orbit coupling of Cl 2p3/2 and Cl 2p1/2
Thus the immobilization does not destroy the basic skeletal of g-
C3N4. However, magnified HR-TEM image shows the high
dispersion of Cu in the g-C3N4 support (Figure 4c-d). Additionally,
the ICP-AES analysis also confirmed the presence of copper in
the immobilized material.
The X-ray photoelectron spectroscopy (XPS) was performed, to
check the composition on the surface of the materials and
oxidation states of the materials (Cu@g-C3N4). The full survey of
XPS spectrum (Figure 5e) displays that C, N, Cu and Cl
elements presence in the material, which is also well
accordance with the SEM-EDAX (Figure 3d). The peak at
283.10 eV in C 1s is attributed to the surface adventitious
carbon and other peak allocated at 286.8 eV is due to the sp3-
hybridized carbon bonded with N-C=N of polymeric graphitic g-
C3N4 (Figure 5a) [93]. For N 1s, four distinguished peaks were
observed. The peak at 397.10 eV has assigned for the nitrogen
(N-C-N), like pyridinium-nitrogen and peak corresponding to
398.6 eV is due to the nitrogen N-(C)3 (Figure5b) [93].
respectively.
The
XPS
studies
reflect
that
amine
functionalization in g-C3N4 offered sufficient stability of CuCl2 in
the surface of the catalyst and could prevent the oxidation of the
metal composite.
Next, we have investigated the catalytic activity of Cu@g-C3N4 in
the synthesis of 4-aryl-NH-1,2,3-triazole (3a) by the reaction of
-nitrostyrene and sodium azide as a model reaction. When a
mixture of -nitrostyrene (1 mmol), sodium azide (3 mmol) and
Cu@g-C3N4 (20 mg) in DMF (2 ml) was heated at 120 oC (Table
1, entry 1) good yield of (82%) of product was observed after 45
min. and no further significant improvement of yield was
observed up to 2 h (Table 1, entries 1-2). Water is proved to
best solvents (entry 3, Table 1) giving 99% of product in 30
minutes among other tested (entries 4-7, Table 1). Next, we
have also screened the reaction using different metal supported
g-C3N4 catalyst such as, Zn@g-C3N4, Ni@g-C3N4, Fe@g-C3N4,
Co@g-C3N4 etc.
Among them, only Zn/Fe@g-C3N4 could produce moderate yield
of product (3) (entries 8-9, Table 1) whereas Ni/Co-@g-C3N4
could not initiate the reaction event after 2 h (entries 10-11,
Table 1). It was also observed that Cu(0)@g-C3N4 produced
product marginally (entry 13, Table 1). Further, the amount of
Cu@g-C3N4 was optimized to 15 mg (entries 16-17, Table 1)
and varying amounts of sodium azide (NaN3) it was observed
that 2 equiv. of NaN3 provided maximum yields (entries 18-19,
Table 1). We have also checked the reaction condition by using
CuCl2 and Cu (0) nanoparticles, which yielded 23 % and 62 % of
the isolated product (entries 20-21, Table 1). Thus, a mixture of
-nitrostyrene (1 mmol), NaN3 (2 mmol) and Cu@g-C3N4 (15 mg)
2 mL of water under refluxing conditions for 30 min. was
considered as optimized reaction conditions (entry 18, Table1).
N-C=N
N-C=N
1200
1000
800
600
400
200
0
2000
1500
1000
500
0
C-C
N-(C)3
C-N-H
408
406
404
402
400
398
396
394
392
292
290
288
286
284
282
280
278
Binding Energy (eV)
Binding Energy (eV)
325
320
315
310
305
300
295
290
Cu2p
3/2
36
33
30
27
Cl 2p
3/2
2+
Strong Cu
Satellite
Cl 2p
1/2
Cu2p
1/2
2+
Strong Cu
Satellite
208
206
204
202
200
198
196
194
970
960
950
940
930
Binding Energy (eV)
Binding Energy (eV)
14000
12000
10000
8000
6000
4000
2000
0
Table 1. Optimization of the reaction conditions for the synthesis of 4-
aryl-NH-1,2,3-triazole.a
Entry
Catalyst
Solvent
Temp (oC)
Time
Yield (%)b
1200
1000
800
600
400
200
Binding Energy (eV)
1
2
3
Cu@g-C3N4
Cu@g-C3N4
Cu@g-C3N4
DMF
DMF
H2O
120 oC
120 oC
100 oC
45 min
2 h
82 %
85 %
99 %
Figure 5. XPS analysis of (a) core level spectra C 1s; (b) core level spectra N
1s; (c) core level spectra Cu 2p; (d) core level spectra Cl 2p; (e) XPS survey
spectrum of Cu@g-C3N4.
30 min
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4
Cu@g-C3N4
Cu@g-C3N4
Cu@g-C3N4
Cu@g-C3N4
Zn@g-C3N4
Fe@g-C3N4
Ni@g-C3N4
Co@g-C3N4
g-C3N4
DMSO
EtOH
MeOH
CH3CN
H2O
120 oC
80 oC
65 oC
2 h
2 h
2 h
2 h
2 h
2 h
2 h
2 h
2 h
2 h
35 %
31 %
24 %
27 %
49 %
39 %
-
5
6
7
65 oC
8
100 oC
100 oC
100 oC
100 oC
100 oC
100 oC
9
H2O
3d; 91 %
3e; 94 %
3f; 98 %
10
11
12
13
H2O
H2O
-
H2O
-
Nano Cu(0)@
g-C3N4
H2O
56 %
14
15
16
17
18
19
20
21
Cu@g-C3N4
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
R.T.
80 oC
2 h
Trace
91 %
99 %c
93 %d
99 %e
67 %f
23 %
62 %
Cu@g-C3N4
Cu@g-C3N4
Cu@g-C3N4
Cu@g-C3N4
Cu@g-C3N4
CuCl2
2 h
100 oC
100 oC
100oC
100 oC
100 oC
100 oC
30 min
30 min
30 min
30 min
30 min
30 min
3g; 95 %
3h; 93 %
3i; 94 %
Cu (0) NPs
aReaction conditions: -nitrostyrenes (0.50 mmol), sodium azide (1.50 mmol),
Cu@g-C3N4 (20 mg) in 2 mL solvent under air. bThe denoted yields corresponds
3j; 98 %
3k; 90 %
3l; 96 %
c
to their pure isolated products. 15 mg of Cu@g-C3N4, d10 mg of Cu@g-C3N4, e2
equiv. of NaN3 and f1 equiv. of NaN3.
Next, using optimized reaction conditions and following a
simple experimental procedure (see SI) we have explored the
scope of the methodology for the synthesis of 4-aryl-NH-1,2,3-
triazole derivatives. It was established that various -
nitrostyrenes with different substituents were well tolerated
under the optimized reaction conditions. The results were
presented in Table 2. Excellent yields of products (90-99 %)
were observed within very short reaction time (30-45 min).
Electron donating group like, -Me, -OMe, -OH and withdrawing
group like, -NO2, -Cl, -Ar present in the aromatic ring of at -
nitrostyrenes were participated smoothly under the reaction
conditions. Moreover, bicycle -nitrostyrene (3i, Table 2) was
also participated in the reaction under same conditions. The
intrinsic nitrogen skeletal of g-C3N4 offers the slightly basic
atmosphere in the reaction media to initiate the reaction without
the using an external base which is required to complete the
conversion. All the reactions listed in Table 2 were very clean
and high yielding. The products were purified by simply short
column chromatography over silica gel.
3m; 90 %
3n; 95 %
3o; 93 %
3p; 97 %
Reaction conditions: -nitrostyrenes (1.0 mmol), sodium azide (2.0 mmol;
4.0 mmol for 3o), Cu@g-C3N4 (15 mg) in 2 mL water at 80 oC for 45 min under
air. The yields refer to those of pure and isolated products.
Next we have investigated the stability and recyclability of the
Cu@g-C3N4 catalyst by considering the synthesis of 4-phenyl-
1H-1,2,3-triazole (3a, Table 2) as a model reaction under
optimized conditions. After each cycle, Cu@g-C3N4 was
recovered simply by filtration, washed thoroughly by ethanol,
dried in oven at 80 oC for 2 h and finally reused for the
subsequent reactions. It was observed that the Cu@g-C3N4 was
very stable under the reaction conditions and recycled up to ten
times with a minimal lose in yields of the product (Figure 6). This
slight decrease in yield was probably due to the leaching of very
nominal amount of metal (about 0.08%) after 10th cycle from the
g-C3N4 support as evident from the inductive-coupled plasma
atomic emission spectroscopic (ICP-AES) analysis. However,
the graphitic nature of the g-C3N4 after 10th cycle remained
unchanged as seen in the powder XRD pattern (SI, Figure 1)
and HR-TEM image of the recovered catalyst (SI, Figure 2).
Table 2. Substrate scope for the synthesis of 4-aryl-NH-1,2,3-triazoles
from -nitrostyrenes and sodium azide.
3a; 99 %
3b, 99 %
3c; 98 %
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92
69
46
23
0
5m, 92 %
Reaction Conditions: Phenylacetylenes (0.5 mmol), sodium azide (0.75
mmol; 1.5 mmol for 5i), Cu@g-C3N4 (15 mg) in 2 mL water at 100 oC for 45
min under air. The yields refer to those of pure and isolated products.
When a mixture of phenyl acetylene (0.5 mmol), sodium azide
(0.75 mmol) and Cu@g-C3N4 (15 mg) was refluxed at 100 C in
o
water excellent yield (92 %) of 4-aryl-NH-1,2,3-triazole (5a,
Table 3) was obtained within 45 minutes. Next, using standard
conditions and following a simple experimental procedure (see
SI), we have synthesized various 4-aryl-NH-1,2,3-triazole
derivatives (5a-l, Table 3) using different phenyl acetylene
derivatives. Moreover, we observed that 1,4-diethynyl benzene
was participated in the reaction smoothly under same reaction
conditions and provided two triazole ring (5i; Table 3).
1
2
3
4
5
6
7
8
9
10
Number of Cycle
Figure 6. Reusability of Cu@g-C3N4 for the synthesis of 4-phenyl-1H-1,2,3-
triazole (3a, Table 2).
Motivated by the excellent catalytic activity of Cu@g-C3N4 in
synthesis of 4-aryl-NH-1,2,3-triazoles, we have extended the
scope of this methodology by using phenyl acetylenes as
substrate under the optimized reaction conditions.
Moreover, we have drawn a plausible reaction mechanism for
polymeric
Cu@g-C3N4 catalyzed de-nitrative 1,3-dipolar
cycloaddition of -nitrostyrenes and sodium azide leading to
formation of 4-aryl-NH-1,2,3-triazole scaffolds has been
presented in Scheme 2. The catalytic reaction is going via co-
ordination of -nitrostyrenes in the surface of Cu@g-C3N4
catalyst followed by nucleophilic addition of sodium azide by
triggering of surface Cu. Next step is the elimination of HNO2 []
followed by the formation of NH-1,2,3-triazole.
Table 3. Substrate scope for the synthesis of 4-aryl-NH-1,2,3-
triazoles from phenylacetylenes and sodium azide.
5a; 92 %
5b, 89 %
5c; 95 %
5e; 93 %
5f; 91 %
5d; 94 %
Scheme 2. Plausible reaction mechanism for the Cu@g-C3N4 catalyzed
4-aryl-NH-1,2,3-triazole synthesis.
This present methodology for the synthesis of 4-aryl-NH-1,2,3-
triazoles offered several advantages over previously published
protocol (i) broad substrate scope including various -
nitrostyrenes and phenylacetylenes, (ii) excellent yield of
products, (iii) shorter reaction time, (iv) use of catalytic amount
and reusable Cu@g-C3N4, (v) milder reaction condition of
heating 100 oC, (vi) use of greener solvent water and (vii) no
5g; 90 %
5h; 84 %
5i; 97 %
5j; 89 %
5k; 96 %
5l; 84 %
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additives required to furnished the reactions which made the
protocol environmental benign in nature.
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In summary, Cu@g-C3N4 catalyst was prepared by the
calcination of urea followed by immobilization of CuCl2 and
characterized by powder XRD, HRTEM, FESEM EDAX,
ICP-AES and XPS analysis. The Cu@g-C3N4catalyst
showed excellent activity for the regioselective synthesis of
4-aryl-NH-1,2,3-triazole derivatives via denitrative 1,3-
diipolar cycloaddition reactions of nitroolefins and sodium
azide in good to excellent yields (90-99%) within short
reaction time (0.5 h). This methodology was also applied for
the synthesis of 4-aryl-NH-1,2,3-triazole derivatives from
phenyl acetylene derivatives. The present protocol offered
several advantages such as: (i) use of very stable and
novel Cu@g-C3N4 as catalyst, (ii) wide range of substrate
scope including nitroolefins and phenyl acetylenes, (iii)
short reaction time (0.5 h), (iv) excellent yields of 4-aryl-NH-
1,2,3-triazole derivatives, and finally, (v) use of water as
reaction medium and reusability of catalyst made the
protocol environmental-friendly in nature. To the best of our
knowledge this is the first report of preparation of polymeric
g-C3N4@Cu composite and its applications in useful “click
reactions”.
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Supporting Information Summary
Preparation procedures and characterizations of the
catalysts, reusability of the catalyst and representative NMR
copies will be available in the supporting information.
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We are pleased to acknowledge funding agency CCOST, Raipur
(ENDT No 2096/CCOST/1I[RP/2017). Special thanks to Prof. B.
C. Ranu and his research group for their help in NMR and
powder XRD, FT-IR, FE-SEM, HR-TEM studies. We are also
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Keywords: 4-aryl-NH-1,2,3-triazole • Heterogeneous catalysis •
polymeric g-C3N4@Cu composite • Click reactions • Green
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Entry for the Table of Contents
Here, we have developed of graphitic polymeric C3N4 supported CuCl2 (Cu@g-C3N4) material for efficient and regioselective on water
synthesis of 4-aryl-NH-1,2,3-triazole derivatives via 1,3-diipolar cycloaddition reactions of nitroolefins/phenylacetylenes to sodium
azide.
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