Copper(II) bis-thiazole complex immobilized on silica nanoparticles: Preparation, characterization and its application as a highly efficient catalyst for click synthesis of 1,2,3-triazoles

Article abstract of DOI:10.1016/j.poly.2017.08.032

In this work, the preparation of copper(II) complex of 3,5-bis(2-benzothiazolyl)pyridine, Cu(II)Br₂-BTP, supported on nano silica functionalized with trimethoxysilylpropylchloride, Cu(II)Br₂-BTP@TMSP-nSiO₂, is reported. Th

Full text of DOI:10.1016/j.poly.2017.08.032

Accepted Manuscript
Copper(II) bis –thiazole complex immobilized on silica nanoparticles: Prepa-
ration, characterization and its application as a highly efficient catalyst for click
synthesis of 1,2,3–triazoles
Zahra Dehbanipour, Majid Moghadam, Shahram Tangestaninejad, Valiollah
Mirkhani, Iraj Mohammadpoor–Baltork
PII:
S0277-5387(17)30563-6
DOI:
http://dx.doi.org/10.1016/j.poly.2017.08.032
POLY 12796
Reference:
Polyhedron
To appear in:
Received Date:
Accepted Date:
2 April 2017
23 August 2017
Please cite this article as: Z. Dehbanipour, M. Moghadam, S. Tangestaninejad, V. Mirkhani, I. Mohammadpoor–
Baltork, Copper(II) bis –thiazole complex immobilized on silica nanoparticles: Preparation, characterization and
its application as a highly efficient catalyst for click synthesis of 1,2,3–triazoles, Polyhedron (2017), doi: http://
dx.doi.org/10.1016/j.poly.2017.08.032
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Copper(II) bis–thiazole complex immobilized on silica nanoparticles:
Preparation, characterization and its application as a highly efficient
catalyst for click synthesis of 1,2,3–triazoles
∗
Zahra Dehbanipour, Majid Moghadam, Shahram Tangestaninejad,* Valiollah Mirkhani,*
Iraj Mohammadpoor–Baltork
Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan 81746–73441, Iran
Abstract– In this work, the preparation of copper(II) complex of 3,5–bis(2–benzothiazolyl)pyridine,
Cu(II)Br2–BTP, supported on nano silica functionalized with trimethoxysilylpropylchloride, Cu(II)Br2–
BTP@TMSP–nSiO2, is reported. The prepared catalyst was characterized by different analytical
1
techniques such as elemental analysis, FT–IR, H NMR, ICP-OES, XPS and UV–Vis spectroscopic
methods, and also SEM and TEM microscopic techniques. This heterogeneous catalyst showed
excellent activity in the click synthesis of 1,2,3–triazoles via one–pot three–component reaction of
alkynes, organic halides, and sodium azide. Moreover, the catalyst was applied for synthesis of 1,2,3–
triazoles by the reaction of α–bromoketones, alkyl/aryl terminal alkynes and sodium azide. The
heterogeneous catalyst was reused several times without any decrease in its catalytic activity.
Keywords: Supported copper catalyst; Click reaction; Bis–Thiazole; 1,2,3–Triazole; Nano–silica.
∗
Corresponding authors: Tel: +98-31-3793-4920; Fax: +98-31-36689732; E-mails: moghadamm@sci.ui.ac.ir (M.
Moghadam); stanges@sci.ui.ac.ir (S. Tangestaninejad); mirkhani@sci.ui.ac.ir (V. Mirkhani).
1

1. Introduction
Thiazole is a five–membered heterocyclic ring with nitrogen and sulfur atoms [1]. Benzothiazole is a
privileged bicyclic ring system which contains a benzene ring fused to a thiazole ring [2]. Bidentate
heterocyclic ligands containing both nitrogen and sulfur atoms possess versatile coordination ability
toward various transition metal ions; as a result, they have attracted considerable interest, particularly
in the synthesis and application of bioactive coordination compounds [3-5].
2–Substituted benzothiazoles play an important role in chemistry, biochemistry and pharmacology [6-
10]. They also have different biological activities such as antitumor [11], antifungal [12], anti–
inflammatory [13], antimicrobial [14], antiviral [15], and enzyme inhibitory activity [16]. But, there are
few reports on the application of thiazole complexes as catalyst. For example, the Pd complex of a bis-
thiazole ligand was used as catalyst in the Suzuki−Miyaura reaction [17, 18].
The concept of “Click chemistry” reported by Sharpless and coworkers in 2001 has revolutionized the
molecular engineering [19] because of its applications in organic and medicinal chemistry [20-29] and
polymer and materials science [30-39]. The most widely used click reaction is the copper(I)–catalyzed
reaction between terminal alkynes and azides (CuAAC) selectively proceeding 1,4–disubstituted 1,2,3–
triazoles, that was reported independently by the Sharpless–Fokin [40] and the Meldal groups in 2002
[41, 42]. 1,2,3–Triazoles are five membered nitrogen containing heterocyclic compounds having
aromatic temperament which are remarkably stable to light, moisture, and oxygen. Various compounds
consisting 1,2,3–triazole moiety show anticancer [43], fungicidal [44], antiviral [45], antiallergic [46],
antibacterial [47] and anti–HIV [48] activities. The first report of this reaction, shows that the active
Cu(I) species were directly synthesized from Cu(I) salts in the presence of ligands [40]. However, the
instability of Cu(I) salts, usually Cu(I) is prepared in situ via reduction of Cu(II) with ascorbate [49] or
by comproportionation of Cu metal and Cu(II) salts [50]. Despite the efficiency of these systems in the
synthesis of 1,2,3–triazoles, using homogeneous copper catalysts may contaminate the isolated desired
2

product [51]. One way to overcome this problem is to immobilize the copper species on different solid
supports such as alumina [52], zeolite [53], magnetic nanoparticles [54], hydrotalcite [55], nano-silica
[56], polysryrene [57] and triazine dendrimer [58].
On the other hands, because of the explosive property of the azides, various procedures for the
preparation of 1,4–disubstituted 1,2,3–triazoles through the in situ generation of organic azides have
been developed [59].
Due to the potential application of bis–thiazoles as ligand for coordination to metals [60], here, we
report the synthesis of 3,5–(bis(2–benzothiazolyl))pyridine by the reaction of 2–aminothiophenol with
3,5–pyridinedicarboxylic acid. This new bis–thiazole ligand was attached to nanosilica functionalized
with trimethoxysilylpropyl chloride and finally reacted with CuBr2. The catalyst was used in the
synthesis of 1,2,3–triazoles by the reaction of acetylene derivatives, benzyl halides or α–bromoketones
and sodium azide (Scheme 1).
Scheme 1. Click reaction catalysed by Cu(II)Br2–BTP@TMSP–nSiO2
2. Results and Discussion
2.1. Synthesis and characterization of catalyst
3

The preparation route of the heterogeneous catalyst is shown in Scheme 2. First, 2–aminothiophenol
was reacted with 3,5–pyridinedicarboxylic acid in the presence of triphenylphosphite, and the 3,5–
(bis(2–benzothiazolyl))pyridine ligand, (BTP), was produced. Reaction of BTP with silica modified
with 3–chloropropyltrimethoxysilane, CPTMS, produced the TMSP–nSiO2 as ligand. Finally, this
ligand was reacted with CuBr2 to give the Cu(II)Br2–BTP@TMSP–nSiO2. The BTP was characterized
by elemental analysis, FT–IR, 1H NMR and UV–Vis spectroscopic techniques. The FT–IR spectrum of
the BTP showed the characteristic band of thiazole ring, (C=N), at 1424 cm–1.
The prepared heterogeneous catalyst was characterized by elemental and thermal analyses, SEM, TEM,
ICP-OES, FT–IR, XPS and UV–Vis spectroscopic techniques.
In the diffuse–reflectance UV–vis spectrum of the BTP@TMSP–nSiO2, the peak at 347 nm was
attributed to n→π∗ transitions in the BTP@TMSP–nSiO2 (Fig. 1). In the case of the Cu catalyst, the
peak at 726 nm was assigned to the d–d transition of Cu ion in Cu(II)Br2–BTP@TMSP–nSiO2 (Fig. 2).
The nitrogen content of the catalyst, determined by CHNS analysis, was about 1.00-1.17 mmol/g
(1.52% 0.12). This value shows that the amount of ligand on the nanosilica is about 0.36 mmol/g.
The Cu loading of the catalyst, measured by ICP, showed a value of about 0.35 mmol/g of Cu(II)Br2–
BTP@TMSP–nSiO2. The CHNS analysis of bare nanosilica showed no absorbed nitrogen on the silica
surface.
The FT–IR spectrum of the heterogeneous catalyst showed the stretching vibration of the Si−O−Si
bond at 1099 and 802 cm–1. Furthermore, the bands at 2959 cm–1 were assigned to C−H stretching
vibrations. Also, the (C=N) vibration band was observed at 1426 cm–1. These observations proved the
supporting of Cu catalyst on nano silica (Fig. 3).
The SEM image showed that the shape of silica nanoparticles is spherical and aggregated (Fig. 4). The
energy dispersive X–ray (EDX) results obtained from SEM analysis for the Cu(II)Br2–BTP@TMSP–
nSiO2, showed the presence of Cu, O, N, C, Si, S Br atoms (Fig. 5). Also, the distribution of the C, O,
4

N, S, Si, Br and Cu is shown by elemental mapping. As can be seen all elements have been distributed
uniformly in the catalyst texture (Fig. 6).
Further characterization of Cu(II)Br2–BTP@TMSP–nSiO2 was performed by transmission electron
microscopy (TEM), that confirmed the nanometer dimensions of the heterogeneous catalyst particles
and also shows that the Cu catalyst has been dispersed on the silica nanoparticles (Fig. 7). As shown in
the particle size histogram, the average size of the nanoparticles is about 30–35 nm (Fig. 8).
In order to know the exact oxidation state of copper in catalyst, Cu(II)Br2–BTP@TMSP–nSiO2 were
characterized by X–ray photoelectron spectroscopy (XPS) (Fig. 9). The elemental survey scan of
Cu(II)Br2–BTP@TMSP–nSiO2 shows the presence of all elements in the catalyst texture (Fig. 9a). In
order to correct possible deviations caused by electric charge of the samples, the C(1s) line at 285.0 eV
was taken as internal standard. The Cu(2p3/2) peak of the catalyst, attributed to Cu2+ species, was
observed at 933.5 eV [61] (Fig. 9b).
Scheme 2. The preparation route for heterogeneous catalyst
2.3. Investigation of catalytic activity of Cu(II)Br2–BTP@TMSP–nSiO2 in the synthesis of 1,2,3–
triazole derivatives
5

The catalytic activity of the heterogeneous catalyst was studied in the synthesis of 1,2,3–triazoles. In
this manner, the reaction of 4–bromobenzyl bromide with phenyl acetylene and sodium azide was
chosen as model reaction and the reaction parameters such as amount of catalyst, the type of solvent
ans also temperature were optimized in this reaction. When the model reaction was carried out in the
absence of catalyst or sodium ascorbate, no product was obtained under these conditions. These results
showed that the presence of catalyst and sodium ascorbate is mandatory in this reaction (Table 1,
entries 13 and 14). As mentioned in our previous work [56], the mechanism of these reactions contains
a copper acetylide copper(I) compound. Therefore, the presence of Cu(I) species is required to react
with phenyl acetylene.
When, the model reaction was performed in the presence of Cu(II)Br2–BTP@TMSP–nSiO2 (0.2 mol%)
and sodium ascorbate (5 mg), the highest yield was obtained. Different solvents were also tested in this
click reaction. Among the mixture of acetonitrile, DMF, methanol, ethanol and t–BuOH with water, the
3:1 ethanol/water mixture was chosen as the reaction medium, because the higher catalytic activity was
obtained. Also, different ratios of ethanol /water mixture were tested and the results showed that the 3:1
mixture of ethanol /water is the best medium for reaction. The effects of amount of the catalyst and
temperature were also investigated; with lowering these parameters the yield of the desired product
decreased. As can be seen, the best result was obtained using 0.2 mol% of the catalyst and 5 mg sodium
ascorbate in ethanol /water mixture, at 85 ºC (Table 1).
The general applicability of this catalyst was examined in the reaction of different alkynes and
substituted benzyl bromides under the optimized reaction conditions. As can be seen in Table 2, both
aromatic and aliphatic terminal acetylenes produced the desired corresponding products in excellent
yields. Compared to aryl alkynes, the reaction times was longer for aliphatic counterparts. To show the
effect of immobilization of BTP on nanosilica, the model reaction was carried out in the presence of
0.2 mol% of homogeneous catalyst. In this case, the corresponding triazole was produced in 63% yield.
6

The higher catalytic activity of heterogeneous catalyst may be due to the dispersion of Cu(II) species
on high surface area nanosilica. It is noteworthy that the nature of the substituent on the benzyl bromide
has no significant effect on the yield of the products.
The ability of this catalyst in the synthesis of 1,4–disubstituted 1,2,3–triazoles using α–bromo ketones
was also tested. Different α–bromo ketones were reacted with terminal alkynes and sodium azide in the
presence of Cu(II)Br2–BTP@TMSP–nSiO2 and sodium ascorbate to produce the corresponding β–
keto–1,2,3–triazoles in 80–95% yields at 85 ºC (Table 3, entries 1–5).
Bis–triazoles have been used as ligand in coordination chemistry [62, 63], and as precursors for ionic
liquids [64, 65]. Therefore, their preparation is of great importance. In this manner, the catalytic
activity of the Cu(II)Br2–BTP@TMSP–nSiO2 was investigated in the "bis–click" reaction of 1,2–
bis(bromomethyl)benzene or 1,4–bis(bromomethyl)benzene with terminal alkynes and sodium azide at
º
85 C, and the corresponding bis–1,2,3–triazoles were obtained in excellent yields. The results are
shown in Table 4.
2.4. Recycling of the Cu(II)Br2–BTP@TMSP–nSiO2 catalyst
In the field of heterogeneous catalysis, the catalyst recovery and reuse is very important from
practical, economic and environmental points of view. Thus, the reusability of Cu(II)Br2–
BTP@TMSP–nSiO2 was investigated in the reaction of 4–bromobenzyl bromide (1 mmol) with
phenyl acetylene (1 mmol), sodium azide (1.2 mmol) and in the presence of Cu(II)Br2–
BTP@TMSP–nSiO2 catalyst (0.2 mol%) at 85 °C for 30 min. After completion of reaction, the
catalyst was separated from the reaction mixture by simple filtration, washed with methanol and dried
carefully before using it in the subsequent run. The reaction times and conditions for reused
catalyst were as same as fresh one. The obtained results revealed that the catalyst was reusable
for five successive times without detectable decrease in its catalytic activity (Fig. 10). The
7

analysis of the filtrates for determining the amount of copper leached from Cu(II)Br2–BTP@TMSP–
nSiO2 catalyst by ICP showed that about 4% of initial copper content was leached in the first run.
No copper was detected in the filtrates of the next runs. This fact shows the strong attachment
of the copper catalyst to the nanosilica.
3. Experimental Section
3.1. General Remarks
The chemicals were purchased from Fluka and Merck chemical companies. Fourier transform infrared
(FT-IR) spectra were obtained in transmission mode using KBr pellets by a JASCO 6300D
1
spectrophotometer. H (400 and 100 MHz) spectra were recorded on a Bruker Avance 400 MHz
spectrometer using CDCl3 as solvent. Elemental analysis was performed on a LECO CHNS–932
analyzer. The UV-vis spectra were recorded by a JASCO V-670 spectrophotometer. The scanning
electron micrographs were taken on a Hitachi S–4700 field emission–scanning electron microscope
(FE–SEM). The transmission electron microscopy (TEM) was carried out on a Philips CM10
transmission electron microscope operating at 100 kV. The X–ray photo–electron spectroscopy (XPS)
measurements were performed using a Gammadata–scienta ESCA200 hemispherical analyzer equipped
with an Al (Kα= 1486.6 eV) X–ray source. The Cu contents in the catalysts were determined using
inductively coupled plasma optical emission spectrometry (ICP-OES) a Jarrell-Ash 1100 ICP analyzer.
The silica nanoparticles were prepared, activated and chloropropylated by known procedures [56, 66,
67].
3.2. Synthesis of the 3,5–bis(2–benzothiazolyl)pyridine (BTP) ligand
In a 25 mL round bottomed flask equipped with a condenser, a mixture of triphenyl phosphite (TPP,
0.52 ml, 2 mmol), tetrabutylammonium bromide (TBAB, 0.88 g, 3 mmol), 2–aminothiophenol (0.212
ml, 2 mmol), and pyridine–3,5–dicaboxylic acid (0.164 g, 1 mmol) was prepared and stirred at 100 ºC
8

for 120 min. At the end of the reaction, MeOH (15 ml) was added to the viscous solution to precipitate
the product. The resulting solid was filtered off and washed with cold MeOH to give the desired 3,5–
bis(2–benzothiazolyl)pyridine (BTP) ligand. Then, residue was purified by recrystallization from
ethanol to afford the pure product.1H NMR (400 MHz, CDCl3) 9.42 (d, J = 2Hz, 2H), 9.06 (t, J = 2.4,
1H), 8.18 (d, J = 8.4, 2H), 8 (dd, J = 8, 0.4Hz, 2H), 7.59 (td, J = 8.2, 0.26 Hz, 2H), 7.47–7.51 (td, 2H,
aromatic H), FT–IR (KBr disc): 1690 (s), 1417 (m), 1265 (s), 957 (m), 751 (s), 720 (s), cm–1. Elemental
analysis: calcd for C20H12N2S2 (344) C, 69.76; H, 3.49; N, 8.17; S, 18.62; found: C, 71.39; H, 3.79; N,
7.75; S, 18.66.
3.3. Immobilization of 3,5–bis(2–benzothiazolyl)pyridine (BTP) ligand on nano–SiO2, BTP@TMSP–
nSiO2
A solution of BTP ligand (0.1 g, 0.4 mmol) in DMF (10 mL) was prepared in a round–bottomed flask
equipped with a condenser and a magnetic stirrer bar. Silica nanoparticles (1 g) were added to this
solution, and the suspension was stirred at 80 ˚C for 24 h. At the end of the reaction, the mixture was
filtered and washed with CHCl3 (2×10 mL) to remove the non–immobilized ligand. The resulting solid
was dried in a vacuum oven at 50 ˚C.
3.4. Preparation of Cu(II)Br2–BTP@TMSP–nSiO2 catalyst
A mixture of BTP@TMSP–nSiO2 ligand (1 g) and CuBr2 (1.5 mmol) was stirred at 60 ˚C in MeOH for
24 h. In order to assure that no Cu is adsorbed on the surface, the particles were repeatedly washed with
o
MeOH and finally dried at 50 C. The Cu content of the catalyst was determined using ICP-OES
analysis.
3.5. General procedure for synthesis of 1,2,3–triazoles from benzyl bromides
A mixture of Cu(II)Br2–BTP@TMSP–nSiO2 (0.2 mol%, 10 mg) and sodium ascorbate (5 mg) in
ethanol/water (3:1) (2 mL) was stirred for 2 min and then, benzyl bromide (1 mmol), sodium azide (1.2
mmol) and alkyl/phenyl acetylene (1 mmol) were added to the mixture. The reaction mixture was
9

heated at 85 oC. The reaction progress was checked by TLC (eluent n–hexane/ethyl acetate, 2:1). At the
end of the reaction, the mixture was diluted with water and ethyl acetate. The catalyst was removed by
simple filtration, washed with acetone and water, and dried under vacuum. The organic layer was dried
over Na2SO4. The products were purified by recrystallization from n–hexane/EtOAc
3.6. General procedure for synthesis of 1,2,3–triazoles from α–bromo ketones
A mixture of Cu(II)Br2–BTP@TMSP–nSiO2 (0.2 mol%, 10 mg) and sodium ascorbate (5 mg) in
ethanol/water (3:1) (2 mL) was stirred for 2 min and then α–bromo ketone (1 mmol), sodium azide (1.2
mmol) and alkyl/phenyl acetylene (1 mmol) were added to mixture. The reaction mixture was stirred at
85 ˚C. The reaction progress was monitored by TLC (elutent n–hexane /ethyl acetate, 1:1). After
completion of the reaction, the desired products were isolated according to the workup procedure
described above. If necessary, purification of product was performed by recrystallization from n–
hexane/EtOAc.
3.7. General procedure synthesis of bis 1,2,3–triazoles
A mixture of Cu(II)Br2–BTP@TMSP–nSiO2 (0.4 mol%, 20 mg) and sodium ascorbate (10 mg) in
ethanol/water (3:1) (3 mL) was stirred for 2 min, and then 1,4 /1,2–bis(bromomethyl)benzene (1
mmol), sodium azide (2.4 mmol) and alkyl/phenyl acetylene (2 mmol) were added to mixture. The
purification and isolation of the product was as same as the procedure described above.
3.8. Synthesis of homogeneous catalyst
In a 25 mL round bottomed flask equipped with a condenser, a mixture of triphenylphosphite (TPP,
0.52 ml, 2 mmol), tetrabutylammonium bromide (TBAB, 0.88 g, 3 mmol), 2–aminothiophenol (0.212
ml, 2 mmol), and 1,3-benzenedicarboxylic acid (0.164 g, 1 mmol) was prepared and stirred at 100 ºC
for 120 min. At the end of the reaction, MeOH (15 ml) was added to the viscous solution to precipitate
the product. The resulting solid was filtered off and washed with cold MeOH to give the desired 1,3-
bis(2-benzothiazolyl)benzene(BTB) ligand. Then, residue was purified by recrystallization from ethanol
10

to afford the pure product. 1H NMR (400 MHz, CDCl3) 8.83 (t, J = 1.6, 1H), 8.25 (dd, J = 7.6, 1.6 Hz,
2H), 8.15 (d, J = 8, 2H), 7.97 (dd, J = 8, 0.4 Hz, 2H), 7.66 (t, J = 8, Hz, 1H), 7.53‒7.58 (td, 2H,
aromatic H ), 7.43‒7.47 (td, 2H, aromatic H), FT–IR (KBr disc): 1690 (s), 1417 (m), 1265 (s), 957 (m),
751 (s), 720 (s), cm–1. Elemental analysis: calcd for C20H12N2S2 (344) C, 69.76; H, 3.49; N, 8.17; S,
18.62; found: C, 71.39; H, 3.79; N, 7.75; S, 18.66.
A mixture of 0.34 g (1 mmol) 1,3-bis(2-benzothiazolyl)benzene(BTB) ligand and 0.22 gr (1 mmol)
CuBr2 was stirred at reflux in a 10 mL EtOH for 5 hours. After the homogeneous catalyst were
synthesized, the resulting solid was filtered off and washed with EtOH to give the desired Cu(II)Br2-
BTB complex. FT–IR (KBr disc): 1432 (m), 1209 (s), 752 (m), 718 (m) cm–1.
4. Conclusions
In conclusion, we have developed a novel copper–containing bis(thiazole) ligand immobilized on silica
nanoparticles, Cu(II)Br2–BTP@TMSP–nSiO2, for synthesis of 1,4–disubstituted–1,2,3–triazoles via
one pot three–component reaction of substituted benzyl bromides, sodium azide and terminal alkyne.
This procedure was applicable for both aromatic/aliphatic acetylenes and benzyl bromide/α–bromo
ketones, and the corresponding triazoles obtained in excellent yields. Also, bis 1,4–disubstituted–1,2,3–
triazoles were synthesized by this catalytic system. The noteworthy features of this catalytic system are
high catalytic activity, ease of separation and reusability of the catalyst, and environmentally benign
reaction conditions. This heterogeneous catalyst was reused five consecutive times without significant
loss of its activity.
11

Table 1. Optimization of conditions in the reaction of 4–bromobenzyl bromide with phenylacetylene.
Entry
1
Catalyst amount (mol%)
Solvent
MeOH
T (˚C)
85
Time (min) Yield (%)a
0.2
0.2
0.2
0.2
0.2
0.1
0.2
0.3
0.2
0.2
0.2
0.2
–
30
30
30
30
30
45
30
30
30
30
30
30
30
30
64
61
2
Ethanol
85
3
DMF
85
55
4
t–BuOH/H2O (3:1)
Acetonitrile
85
42
5
65
85
6
EtOH/H2O (3:1)
EtOH/H2O (3:1)
EtOH/H2O (3:1)
EtOH/H2O (3:1)
EtOH/H2O (3:1)
EtOH/H2O (1:1)
EtOH/H2O (2:1)
EtOH/H2O (3:1)
EtOH/H2O (3:1)
85
71
7
85
95
8
85
95
9
65
81
10
11
12
13
14b
45
73
85
65
85
75
85
–
0.2
85
Trace
aIsolated yield.
bWithout sodium ascorbate.
12

Table 2. Three–component synthesis of 1,4–disubstituted 1,2,3–triazoles from benzyl bromides
catalyzed by Cu(II)Br2–BTP@TMSP–nSiO2.
13

Entry
1
Ar
R
Product
Time (min)
30
Yield (%)a
4‒BrC6H4
96
Ph
Ph
2
3
4‒NO2C6H4
30
25
94
98
3,5‒(CH3)2C6H3
Ph
4
5
Ph
C6H13
30
40
95
95
4‒BrC6H4
C6H13
6
7
4‒NO2C6H4
C6H13
45
40
95
93
Ph
C5H11
14

8
9
4‒BrC6H4
C5H11
43
45
94
98
4‒NO2C6H4
C5H11
aIsolated yield.
15

Table 3. Three–component synthesis of 1,4–disubstituted 1,2,3–triazoles from α–bromo ketones.
Entry
1
Ar
R
Product
Time (min)
25
Yield (%)a
98
4‒BrC6H4
Ph
2
3
4
4‒NO2C6H4
4‒FC6H4
Ph
Ph
30
25
25
87
97
96
3‒MeOC6H4
C5H11
5
6
4‒cyclohexylC6
C5H11
45
30
92
90
H4
2‒Furyl
Ph
aIsolated yield.
16

Table 4. Three–component synthesis of 1,4–disubstituted 1,2,3–triazoles from 1,2–bis(bromomethyl)
and 1,4–bis(bromomethyl)benzene catalyzed by Cu(II)Br2–BTP@TMSP–nSiO2.a
Organic halide
Alkyne
Product
Br
Br
Br
Br
aReaction conditions: Organic halide (1 mmol), alkyne (2 mmol), sodium azide (2.4 mmol), Cu(II)Br2–
BTP@TMSP–nSiO2 (0.4 mol%), sodium ascorbate (10 mg) in Ethanol/H2O (3:1) (5 ml) at 85 ˚C.
bIsolated yield.
17

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Fig. 1. Diffuse–reflectance UV–vis spectrum of the BTP@TMSP–nSiO2
22

Fig. 2. Diffuse–reflectance UV–vis spectrum of the Cu(II)Br2–BTP@TMSP–nSiO2
23

Fig. 3. The FT–IR spectra of: a) Cu(II)Br2–BTP@TMSP–nSiO2; b) BTP@TMSP–nSiO2; c) TMSP–
nSiO2
24

,
Fig. 4
25

. SEM images of catalyst.
26

Fig. 5.EDX spectrum of catalyst
27

Cu Ka1
C Ka1
S Ka1
O Ka1
N Ka1
Si Ka1
28

Br Ka1
Fig. 6. Elemental Mapping of The catalyst
Fig. 7. TEM image of catalyst
29