Preparation of Cu(OAc)2/MCM-41 catalyst and its application in the one-pot synthesis of 1,2,3-triazoles in water

Article abstract of DOI:10.1002/hc.21031

An efficient one-pot synthesis of 1,2,3-triazoles via the three-component coupling reaction between benzyl or alkyl bromides, terminal alkynes, and sodium azide in the presence of catalytic amounts of Cu(OAc)₂/MCM-41 catalyst has been described

Full text of DOI:10.1002/hc.21031

Heteroatom Chemistry
Volume 00, Number 0, 2012
Preparation of Cu(OAc) /MCM-41 Catalyst
2
and Its Application in the One-Pot Synthesis of
1,2,3-Triazoles in Water
Rahman Hosseinzadeh,1 Hamid Sepehrian,2 and
Farshid Shahrokhi,1
1Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
2Jaber Ibn Hayan Research Laboratories, Nuclear Science and Technology Research Institute, PO
Box 11365/8486, Tehran, Iran
Received 27 December 2011
copper catalysts have been reported for the con-
ABSTRACT: An efficient one-pot synthesis of 1,2,3-
struction of 1,2,3-triazoles. The “click” chemistry re-
triazoles via the three-component coupling reaction
ported by the Sharpless group described that the
between benzyl or alkyl bromides, terminal alkynes,
Cu(I)-catalyzed cycloaddition can be conducted at
and sodium azide in the presence of catalytic amounts
room temperature and results in 1,4-disubstituted
of Cu(OAc)2/MCM-41 catalyst has been described.
triazoles in high regioselectivity [7]. The required
This catalyst showed high catalytic activity and 1,4-
copper(I) catalysts are usually prepared by in situ re-
regioselectivity for the [3 + 2]Huisgen cycloaddition.
duction of copper(II) salts with ascorbate [8], or by
This method avoids isolation and handling of organic
comproportionation of copper(0) and copper(II) [9].
azides, using water as a solvent, and catalyst recycling
The search for alternative cleaner, safer, and en-
ꢀ
C
makes this synthesis a truly green procedure.
2012
vironmentally friendly technologies is one of the pri-
orities in chemistry. With this objective, the reduc-
tion of wastes, environmentally friendly reagents,
and catalysts are important parameters to achieve
more sustainable processes [10,11].
Wiley Periodicals, Inc. Heteroatom Chem 00:1–7, 2012;
View this article online at wileyonlinelibrary.com. DOI
10.1002/hc.21031
Reusable heterogeneous catalysts have attracted
a great deal of interest in recent years [12]. Since
most of the catalysts are expensive and contaminate
the environment, the development of efficient meth-
ods for recovery and reuse of the catalysts is a very
important aspect in this chemistry. Among various
solid supports, silica is usually preferred. With the
discovery of the MCM-41-type materials [13], new
possibilities for the development of better catalysts
supported on siliceous materials have become avail-
able [14]. These materials have a high surface area
(∼ 1000 m2 g−1), a large pore volume, and an ordered
hexagonal pore array with pore diameters that can
INTRODUCTION
N-Heterocyclic compounds such as 1,2,3-triazoles
have shown important biological activities, and nu-
merous examples are reported in the literature in-
cluding anti-HIV activity [1,2], antibacterial activity
[3], antiallergic activity [4], and selective β3 adrener-
gic receptor agonism [5]. 1,2,3-Triazoles have also a
range of important applications in industries such as
dyes, corrosion inhibition, photostabilizers, photo-
graphic materials, and agrochemicals [6]. Recently,
Correspondence
to:
Rahman
Hosseinzadeh;
e-mail:
r.hosseinzadeh@umz.ac.ir.
Contract grant sponsor: Research Council of University of
˚
be tuned between 20 and 100 A.
Here we wish to report an efficient, safe,
and green one-pot synthesis of 1,4-disubstituted
Mazandaran.
c
ꢀ
2012 Wiley Periodicals, Inc.
1

2
Hosseinzadeh et al.
1
R
alyzed by the copper(I) catalyst in water, stirring at
room temperature and 90◦C for 1 h and 15 min, and
1-benzyl-4-phenyl-1H-1,2,3-triazole was obtained in
95% and 98% yield, respectively (Table 1, entries 1–
2). Further increasing the amount of catalyst did not
improve the yield and the reaction time (Table 1, en-
try 3). The optimum amount of catalyst was 0.04 g
as shown in Table 1 (entries 4–5). When benzyl bro-
mide, sodium azide, and phenylacetylene were re-
acted under similar conditions in the absence of the
catalyst, no product was observed after 24 h (Table 1,
entry 6). During the course of further optimization
of the reaction conditions, various polar and apo-
lar or poorly polar solvents were examined and it
was found that the solvent plays a significant role in
terms of the reaction rate and isolated yield (Table 1,
entries 7–11). As recently reported by other groups
[17], apolar solvents did not allow for any transfor-
mation (Table 1, entries 10–11). Under the same con-
dition, acetonitrile gave only very low yield of the ex-
pected product, whereas the more polar DMF gave
the product in moderate yield (Table 1, entries 7–9).
Water proved to be the solvent of choice with its fast
reaction rate, high yield, cheapness, “green” solvent
nature, and environmental acceptability.
N
Cu(OAc)2 /MCM-41
N
N
R1Br
R2CCH
+
+
NaN3
Sodium ascorbate
H2O
R2
R1=Alkyl, Benzyl
R2=Aromatic, Aliphatic
SCHEME 1
1,2,3-triazoles from benzyl and alkyl bromides,
sodium azide, and alkynes catalyzed by MCM-41-
supported copper(II) (Scheme 1). The reactions were
carried out in water as a green, nontoxic, and
nonflammable solvent, which is recently used as a
medium for organic reactions with almost all reac-
tion types explored [15].
RESULTS AND DISCUSSION
The MCM-41-supported copper(II) was readily pre-
pared in two steps. First, MCM-41 was prepared
according to our previously published procedure
[16]. Then, it was treated with copper(II) ac-
etate in ethanol at 35◦C for 8 h to generate the
Cu(OAc)2/MCM-41 catalyst.
To show the generality of this method, we stud-
ied the reaction of benzyl and alkyl bromide with a
variety of terminal alkynes in the presence of sodium
azide under optimum conditions and the results are
presented in Table 2.
For our initial screening experiments, the 1,3-
dipolar cycloaddition reaction between benzyl bro-
mide, sodium azide, and phenylacetylene in a 1:1.1:1
molar ratio was chosen as the model reaction
(Table 1).
As can be seen from Table 2, all reactions were
highly regioselective toward the 1,4-disubstituted
triazoles and afforded the desired products nearly
in quantitative yields in most cases. For example,
The reaction was carried out simply by mix-
ing alkyne, benzyl, and alkyl bromides and sodium
azide in the presence of a catalytic amount of
Cu(OAc)2/MCM-41 (0.04 g). The mixture was cat-
TABLE 1 Effect of Solvent, Temperature, and Amount of the Catalyst on the One-Pot Synthesis of 1-Benzyl-4-phenyl-1H-
1,2,3-triazolea
Cu(OAc)2/MCM-41
N
N
BnBr
NaN3
PhC CH
Sodium ascorbate
solvent
N
Ph
Bn
Entry
Catalyst (g)
Solvent/Temperature (◦C)
Time (h)
Yield (%)b
1
2
3
4
5
6
Cu(OAc)2/MCM-41 (0.04 g)
Cu(OAc)2/MCM-41 (0.04 g)
Cu(OAc)2/MCM-41 (0.05 g)
Cu(OAc)2/MCM-41 (0.03 g)
Cu(OAc)2/MCM-41 (0.02 g)
No catalyst
H2O/25
H2O/90
H2O/90
H2O/90
H2O/90
1
0.25
0.25
0.25
0.25
24
95
98
98
75
60
–
H2O/90
7
8
9
10
11
Cu(OAc)2/MCM-41 (0.04 g)
Cu(OAc)2/MCM-41 (0.04 g)
Cu(OAc)2/MCM-41 (0.04 g)
Cu(OAc)2/MCM-41 (0.04 g)
Cu(OAc)2/MCM-41 (0.04 g)
DMF/25
DMF/90
CH3CN/25
EtOAc/25
Toluene/25
2
2
24
24
25
40
10
–
24
–
aReagents and conditions: BnBr (1 mmol), PhC≡CH (1 mmol), NaN3 (1.1 mmol), sodium ascorbate (45 mol%, 0.09 g) and catalyst.
bIsolated yield.
Heteroatom Chemistry DOI 10.1002/hc

Preparation of Cu(OAc)2/MCM-41 Catalyst and Its Application in the One-Pot Synthesis of 1,2,3-Triazoles in Water
3
TABLE 2 One-Pot Synthesis of 1,4-Disubstituted 1,2,3-Triazoles from Benzyl or Alkyl Halides, Sodium Azide, and Alkynesa
Entry
Halide
Alkyne
Productb
Time (h)
Yield (%)c
N
N
Ph
N
Ph
1
2
PhCH2Br
PhC≡CH
PhC≡CH
0.25
0.33
98
98
N
N
Br
N
Ph
4-BrPhCH2Br
N
N
6
N
N
N
N
Ph
Ph
3
4
Br(CH2)6Br
PhCH2Br
PhC≡CH
2
95
98
N
N
N
Ph
Fe
Fe
1.25
N
N
N
Fe
Fe
Br
5
4-BrPhCH2Br
1.5
95
N
HO
Ph
N
HO
N
Ph
Fe
Ph
Fe
6
7
PhCH2Br
PhCH2Br
0.5
0.5
93
98
N
N
Ph
OH
Ph
N
OH
Ph
Ph
Ph
N
N
Br
OH
OH
N
Ph
Ph
Cl
Cl
8
9
4-BrPhCH2Br
4-BrPhCH2Br
0.75
1.17
98
98
N
N
Br
Br
OH
CH3
N
OH
H3C
N
H3C
CH3
N
OH
OH
OH
N
10
4-BrPhCH2Br
0.33
95
N
N
OH
N
11
12
13
PhCH2Br
PhCH2Br
PhCH2Br
0.33
0.25
0.33
95
83
80
N
N
Ph
Ph
N
CO2Me
CO2Et
MeO2CC≡CH
EtO2CC≡CH
N
N
N
N
N
Br
N
CH3
3
14
15
4-BrPhCH2Br
4-BrPhCH2Br
CH3(CH2)3C≡CH
7
70
89
N
N
Br
N
Ph
Ph
12
aReagents and conditions: alkyl or benzyl bromide (1 mmol), terminal alkyne (1 mmol), NaN3 (1.1 mmol), and sodium ascorbate (45 mol%,
0.090 g) catalyzed by Cu(OAC)2/MCM-41 (0.04 g) in water at 90◦C.
bAll products were characterized by spectroscopic data, physical properties, and by comparison with authentic samples.
cYields refer to pure isolated products.
Heteroatom Chemistry DOI 10.1002/hc

4
Hosseinzadeh et al.
when phenylacetylene reacted with benzyl- and 4-
bromobenzyl azides under optimum reaction con-
ditions, the corresponding triazoles were obtained
in 98% yields (Table 2, entries 1–2). The reaction
of phenylacetylene with dibromohexane gave bistri-
azole in excellent yield (Table 2, entry 3). We have
examined the reaction of terminal acetylene contain-
ing a ferrocenyl moiety with benzyl bromides, which
also resulted in the corresponding triazoles in very
good yields but in longer reaction times (Table 3,
entries 4–5). The results presented in Table 2 show
that the method can be successfully used for the re-
action of benzyl azides and a variety of propargyl al-
cohols carrying either aryl substituents (entries 6–8)
or alkyl substituents (entries 9–11). Notably, methyl
and ethyl carboxylate substituted triazoles were also
smoothly obtained in good yields (Table 2, entries
12–13). Moreover, alkylacetylene (1-hexyne) gave
the corresponding 1,2,3-triazole in moderate yield
(Table 2, entry 14). The reaction of 4-bromobenzyl
bromide with alkyne containing a terminal and in-
ternal acetylene moiety showed that this method
is highly selective toward terminal alkyne (Table 2,
entry 15).
The reaction of aryl halide (4-bromoiod-
obenzene) with phenylacetylene was also exam-
ined under optimum conditions, but no product
was formed. But, when 4-bromophenyl azide re-
acted with phenylacetylene, the corresponding tria-
zole was formed in good yield after 15 h (Scheme 2).
These results suggest that an aryl azide cannot
be generated in situ from aryl halide under this
condition.
A good feature of this catalyst is that it can
be recovered and reused several times without loss
of activity. The recyclability of the Cu(OAc)2/MCM-
41 catalyst was examined in the reaction of benzyl
bromide, phenylacetylene, and sodium azide. The
catalyst was recovered by vacuum-filtration onto a
sintered-glass funnel, after washing with CH2Cl2,
and drying at 100◦C overnight. The resulting cata-
lyst was reused without further purification for the
triazole synthesis in a second run of the reaction pro-
cess with the same substrate. This process repeated
for three cycles, and the yield of the triazole did not
change significantly.
CONCLUSION
In conclusion, a safe and efficient three-component
reaction for the regioselective generation of 1,4-
disubstituted 1,2,3-triazoles in water has been de-
veloped. This method avoids isolation and handling
of potentially unstable small organic azides and is se-
lective for the preparation of triazole products from
terminal (not internal) alkynes and alkyl (not aryl)
bromides. Furthermore, Cu(OAc)2/MCM-41 can be
recovered and recycled by simple filtration of the re-
action solution and reused for four consecutive trials
without a decrease in the activity.
EXPERIMENTAL
Synthesis and Characterization of
Cu(OAc)2/MCM-41 Catalyst
MCM-41 was prepared according to our previously
published paper using sodium silicate as a source
of silica and cetyltrimethylammonium bromide as a
structure-directing agent [16]. The Cu(OAc)2/MCM-
41 catalyst was prepared by adding with stirring
the alcoholic solution of copper acetate (200 mg
Cu(OAc)2 in 200 mL of ethanol) to 1 g of MCM-41.
The preparation was kept in ethyl alcohol for 8 h at
35◦C. The material was washed with alcohol and fil-
tered until the filtrate became free from copper ions
and further dried at 120◦C.
The XRD pattern of Cu(OAc)2/MCM-41 shows
three reflections (a very intense peak (100) and two
additional high order peaks (110 and 200) with lower
intensities). This result is characteristic of a hexag-
onal pore structure [18]. The nitrogen adsorption–
desorption isotherm of the sample was obtained at
–196◦C, and specific surface area was determined by
applying the Brunauer-Emmett-Taylor (BET) equa-
tion to the isotherm [19]. The pore size distribution
was calculated using the adsorption branch of the
isotherm and the Barrett-Joyner-Halenda formula
[20]. The nitrogen adsorption–desorption isotherm
of Cu(OAc)2/MCM-41 showed irreversible type IV
adsorption isotherms as defined by IUPAC for meso-
porous materials [18]. The surface area, pore vol-
ume, and pore diameter of Cu(OAc)2/MCM-41 were
2
−1
−1
˚
47.7 m g , 0.15 cc g , and 35.9 A, respectively.
General Procedure for the Preparation of
1,2,3-Triazoles
N
N
X= N3
b
X= I
a
Br
N
X
No Reaction
Br
Ph
To a mixture of alkyl bromide (1 mmol), alkyne (1
mmol), and sodium azide (1.1 mmol) in H2O (5 mL),
the catalyst (0.04 g) and sodium ascorbate (45 mol%,
0.090 g) were added at 90◦C. After completion of
Condition: (a) PhCCH, Cu(OAC)2MCM-41, NaN3, H2O, sodium ascorbate, 90oC
(b) PhCCH, Cu(OAC)2MCM-41, H2O, sodium ascorbate, 90oC
SCHEME 2
Heteroatom Chemistry DOI 10.1002/hc

Preparation of Cu(OAc)2/MCM-41 Catalyst and Its Application in the One-Pot Synthesis of 1,2,3-Triazoles in Water
5
the reaction, as monitored by TLC, dichloromethane
1-(4-Bromobenzyl)-4-ferroceneyl-1H-1,2,
3-triazole (Entry 5 in Table 2)
(15 mL) was added and the reaction mixture was
vacuum-filtered through a sintered glass funnel and
washed with CH2Cl2. The combined organic layer
was washed with water (30 mL) and saturated NaCl
solution (30 mL), dried over anhydrous Na2SO4, and
evaporated in a rotary evaporator. The crude product
was purified by crystallization, using a mixture of n-
hexane and dichloromethane.
mp (◦C) = 174–175; 1H NMR (400 MHz, CDCl3): 4.08
(s, 5H), 4.31 (s, 2H), 4.71 (s, 2H), 5.51 (s, 2H), 7.17
(d, J= 7.6 Hz, 2H), 7.37 (s, 1H), 7.53 (d, J= 7.6 Hz,
2H) ppm; 13C NMR (100 MHz, CDCl3): 53.42, 66.68,
68.77, 69.63, 75.21, 118.65, 122.86, 129.53, 132.32,
133.91, 147.54 ppm; Anal. calcd for C19H16FeN3Br:
C, 54.06; H, 3.82; N, 9.96; found: C, 53.65; H, 3.65;
N, 9.92.
1-Benzyl-4-phenyl-1H-1,2,3-triazole (Entry 1 in
Table 2) [17b]
(1-Benzyl)-1H-1,2,3-triazol-4-yl)(phenyl)
(ferrocenyl)methanol (Entry 6 in Table 2)
mp (◦C) = 133–134; 1H NMR (400 MHz, CDCl3):
5.60 (s, 2H), 7.32–7.44 (m, 8H), 7.70 (s, 1H), 7.83
(d, J= 7.2 Hz, 2H) ppm; 13C NMR (100 MHz, CDCl3):
54.25, 119.61, 125.70, 128.07, 128.18, 128.80, 128.82,
129.17, 130.55, 134.68, 148.23 ppm.
mp (◦C) = 115–116; 1H NMR (400 MHz, CDCl3): 3.76
(s, 1H), 4.13–4.25 (m, 9H), 5.50 (d, J= 14.8 Hz, 1H),
5.53 (d, J= 14.8 Hz, 1H), 7.22–7.45 (m, 11H) ppm;
13C NMR (100 MHz, CDCl3): 53.43, 66.66, 68.22,
68.28, 68.64, 73.23, 121.15, 126.24, 127.17, 127.77,
127.84, 128.71, 129.13, 134.87, 145.29, 155.06 ppm;
Anal. calcd for C26H23FeN3O: C, 69.50; H, 5.16; N,
9.35; Found: C, 69.23; H, 5.01; N, 9.15.
1-(4-Bromobenzyl)-4-phenyl-1H-1,2,3-triazole
(Entry 2 in Table 2) [17b]
mp (◦C) = 156–158; 1H NMR (400 MHz, CDCl3):
5.54 (s, 2H), 7.20 (d, J= 8.4 Hz, 2H), 7.34 (t,
J= 7.4 Hz, 1H), 7.43 (t, J= 7.4 Hz, 2H), 7.53
(d, J= 8.4 Hz, 2H), 7.73 (s, 1H), 7.83 (d, J=
7.2 Hz, 2H) ppm; 13C NMR (100 MHz, CDCl3):
53.59, 118.75, 122.97, 125.69, 128.29, 128.86, 129.67,
130.43, 132.34, 133.71, 147.04 ppm.
(1-Benzyl-1H-1,2,3-triazol-4-yl)
diphenylmethanol (Entry 7 in Table 2) [22]
mp (◦C) = 135–136; 1H NMR (400 MHz, CDCl3):
3.84 (s, 1H), 5.51 (s, 2H), 7.09 (s, 1H), 7.25–7.39
(m, 15 H) ppm; 13C NMR (100 MHz, CDCl3): 54.17,
65.33, 122.41, 127.19, 127.53, 127.89, 128.05, 128.75,
129.13, 134.55, 145.63, 158.44 ppm.
4-Phenyl-1-(6-(4-phenyl-1H-1,2,3-triazol-1-yl)
hexyl)-1H-1,2,3-triazole (Entry 3 in Table 2)
(1-(4-Bromobenzyl)-1H-1,2,3-triazol-4-yl)(4-
chlorophenyl)(phenyl)methanol (Entry 8 in
Table 2)
mp (◦C) = 198–199; 1H NMR (400 MHz, CDCl3):
1.41–1.44 (m, 4H), 1.96–1.99 (m, 4H), 4.42 (t, J= 7.0
Hz, 4H), 7.31–7.37 (m, 2H), 7.42–7.46 (m, 4H), 7.77
(s, 2H), 7.84–7.86 (m, 4H) ppm; 13C NMR (100 MHz,
CDCl3): 25.78, 30.06, 50.09, 119.52, 125.69, 128.17,
128.87, 130.56, 148.23 ppm; Anal. calcd for C22H24N6:
C, 70.94; H, 6.49; N, 22.56; found: C, 70.61; H, 6.37;
N, 22.85.
mp (◦C) = 124–126; 1H NMR (400 MHz, CDCl3): 3.78
(s, 1H), 5.46 (s, 2H), 7.14 (d, J= 8.0 Hz, 2H), 7.28–
7.327 (M, 10H), 7.52 (d, J= 8.8 Hz, 2H) ppm; 13C
NMR (100 MHz, CDCl3): 53.63, 60.33, 76.40, 122.23,
123.04, 127.06, 127.82, 128.22, 128.65, 129.59,
132.37, 133.40, 133.52, 144.10, 145.09, 155.14 ppm;
Anal. calcd for C22H17BrClN3O: C, 58.11; H, 3.77; N,
9.24; found: C, 58.28; H, 3.66; N, 9.05.
1-Benzyl-4-ferroceneyl-1H-1,2,3-triazole (Entry 4
in Table 2) [21]
2-(1-(4-Bromobenzyl)-1H-1,2,3-triazol-4-yl)
propan-2-ol (Entry 9 in Table 2)
mp (◦C) = 158–160; 1H NMR (400 MHz, CDCl3): 4.09
(s, 5H), 4.32 (s, 2H), 4.73 (s, 2H), 5.56 (s, 2H), 7.28–
mp (◦C) = 116–118; 1H NMR (400 MHz, CDCl3): 1.62
(s, 6H), 2.24 (s, 1H), 5.46 (s, 2H), 7.16 (d, J= 8.4 Hz,
2H), 7.37 (s, 1H), 7.52 (d, J= 8.4 Hz, 2H) ppm; 13C
NMR (100 MHz, CDCl3): 30.43, 53.46, 68.54, 119.01,
122.94, 129.77, 132.31, 133.60, 156.22 ppm; Anal.
7.31 (m, 2H), 7.36 (s, 1H), 7.38–7.41 (m, 3H) ppm; 13
C
NMR (100 MHz, CDCl3): 54.07, 66.73, 68.79, 69.73,
75.66, 118.75, 127.89, 128.69, 129.13, 134.93, 147.28
ppm.
Heteroatom Chemistry DOI 10.1002/hc

6
Hosseinzadeh et al.
calcd for C12H14BrN3O: C, 48.67; H, 4.76; N, 14.19;
found:. C, 48.68; H, 4.81; N, 14.18.
53.07; H, 5.48; N, 14.28; found:. C, 53.23; H, 5.30; N,
14.36.
1-(1-(4-Bromobenzyl)-1H-1,2,3-triazol-4-yl)
cyclohexanol (Entry 10 in Table 2)
1-(4-Bromobenzyl)-4-(4-(2-phenylethynyl)
phenyl)-1H-1,2,3-triazole (Entry 15 in Table 2)
mp (◦C) = 128–130; 1H NMR (400 MHz, CDCl3):
1.53–1.96 (m, 10H), 2.00 (s, 1H), 5.47 (s, 2H), 7.16
(d, J= 8.4 Hz, 2H), 7.38 (s, 1H), 7.52 (d, J= 8.4 Hz,
2H) ppm; 13C NMR (100 MHz, CDCl3): 21.93, 25.32,
38.12, 53.47, 69.58, 119.47, 122.91, 129.73, 132.30,
133.68, 156.42 ppm; Anal. calcd for C15H18BrN3O: C,
53.58; H, 5.40; N, 12.50; found:. C, 53.54; H, 5.49; N,
12.46.
1
mp (◦C) = 210–210.5; H NMR (400 MHz, CDCl3):
5.55 (s, 2H), 7.21 (d, J= 8.0 Hz, 2H), 7.36–7.37
(m, 3H), 7.53–7.60 (m, 6H), 7.70 (s, 1H), 7.81 (d,
J= 8.0 Hz, 2H) ppm; 13C NMR (100 MHz, CDCl3):
53.60, 89.19, 90.33, 119.76, 123.06, 123.07, 123.13,
125.57, 125.83, 128.39, 129.70, 130.14, 131.62,
132.11, 132.39, 133.56, 147.82 ppm; Anal. calcd for
C23H16BrN3: C, 66.68; H, 3.89; N, 10.14; found:. C,
66.15; H, 3.70; N, 10.09.
1-(1-Benzyl-1H-1,2,3-triazol-4-yl)cyclohexanol
(Entry 11 in Table 2)
1-(4-Bromophenyl)-4-phenyl-1H-1,2,3-triazole
[23]
mp (◦C) = 125–126; 1H NMR (400 MHz, CDCl3):
1.31–1.94 (m, 10H), 2.70 (s, 1H), 5.48 (s, 2H), 7.25-
7.38 (m, 6H) ppm; 13C NMR (100 MHz, CDCl3):
22.35, 38.08, 40.89, 54.13, 69.47, 119.63, 128.10,
128.69, 129.09, 134.68, 156.14 ppm; Anal. calcd for
C15H19N3O: C, 70.01; H, 7.44; N, 16.33; found:. C,
69.65; H, 7.62; N, 16.68.
mp (◦C) = 232–233; 1H NMR (400 MHz, CDCl3):
7.39–7.43 (m, 1H), 7.47–7.51 (m, 2H), 7.69–7.74 (m,
4H), 7.92–7.94 (m, 2H), 8.20 (s, 1H) ppm; 13C NMR
(100 MHz, CDCl3): δ 117.35, 121.90, 122.43, 125.89,
128.62,128.99, 129.94, 132.97, 136.03, 150.64 ppm.
Recycling of the Catalyst
Methyl 1-benzyl-1H-1,2,3-triazole-4-carboxylate
(Entry 12 in Table 2) [23]
After the reaction had been carried out, the mix-
ture (containing catalyst) was vacuum-filtered onto
a sintered-glass funnel and the residue was washed
with CH2Cl2 (10 mL) and dried at 100◦C overnight
and subjected to a second run of the reaction pro-
cess with the same substrate.
Mp (◦C) = 105–107; 1H NMR (400 MHz, CDCl3): 3.94
(s, 3H), 5.59 (s, 2H), 7.29–7.31 (m, 2H), 7.38–7.42 (m,
3H), 7.99 (s, 1H) ppm; 13C NMR (100 MHz, CDCl3):
52.22, 54.51, 127.38, 128.31, 129.20, 129.35, 133.64,
140.31, 161.10 ppm.
SUPPORTING INFORMATION
Ethyl 1-benzyl-1H-1,2,3-triazole-4-carboxylate
(Entry 13 in Table 2) [24]
Results of characterization of prepared catalysts us-
ing XRD BET methods are available from the cor-
responding author (r.hosseinzadeh@umz.ac.ir) on
request.
Mp (◦C) = 83;1H NMR (400 MHz, CDCl3): 1.39 (t,
J= 7.2 Hz, 3H), 4.41 (q, J= 7.0 Hz, 2H), 5.59 (s,
2H), 7.29–7.31 (m, 2H), 7.38–7.42 (m, 3H), 7.99 (s,
1H) ppm; 13C NMR (100 MHz, CDCl3): 14.30, 54.48,
61.33, 127.32, 128.28, 129.16, 129.33, 133.73, 140.67,
160.71 ppm.
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