6
B. Movassagh, N. Rezaei / Tetrahedron xxx (2014) 1e8
atmosphere. The product formed was filtered off, washed with
ꢁ
EtOH (3ꢃ30 mL) and finally dried in vacuum at 50 C for 24 h.
4.2. General procedure for [3D2] cycloaddition of terminal
alkynes and organic azides
In a 10 mL round-bottom flask, catalyst 2 (20 mg, containing
0
(
.3 mol % of Cu), terminal alkyne (1.0 mmol), organic azide
1.0 mmol), and water (3 mL) were added. The mixture was stirred
at room temperature for 10 h under aerial conditions. Then EtOAc
(
(
5 mL) was added to the mixture, filtered and washed with water
2ꢃ3 mL) and EtOAc (2ꢃ3 mL); the organic layer was separated,
4
dried (MgSO ), and concentrated in vacuum to give the crude
product, which was almost pure.
4
.3. General procedure for the one-pot 3-component syn-
Fig. 6. Recycling activity of the PSeC22eCuI catalyst.
thesis of azides
reactions in water at room temperature. This heterogeneous cata-
lyst can be used for either the Huisgen [3þ2] cycloaddition of al-
kynes and organic azides or one-pot three-component synthesis of
Alkyne (1 mmol), sodium azide (1.1 mmol), organic halide
(1 mmol), and water (3 mL) were placed together in a 10 mL
round-bottom flask. PSeC22eCuI (40 mg, containing 0.6 mol % of
Cu) was then added to the above solution. The suspension was
magnetically stirred for 10 h at room temperature. After com-
pletion of the reaction as followed by TLC, EtOAc (5 mL) was added
to the mixture, filtered, and washed with water (2ꢃ3 mL) and
1,4-disubstituted 1,2,3-triazoles from alkynes, sodium azide, and
alkyl halides at room temperature in water. The catalyst is easily
separated and can be recycled for four runs. Simple preparation of
the complex, oxygen insensitivity, low catalyst loading, and excel-
lent catalytic performance in aqueous media make it a good het-
erogeneous system and a useful alternative to other heterogeneous
copper catalysts.
EtOAc (2ꢃ3 mL). The organic phase was separated, dried (MgSO ),
4
and concentrated in vacuum to give the crude product that was
further purified by recrystallization with ethanol/water (3:1 v/v).
In the case of triazole 5h, after completion of the reaction, water
was evaporated and EtOAc (5 mL) was added. The mixture was
filtered to separate the catalyst and the filtrate was concentrated
under vacuum to obtain the desired product, which was almost
pure.
4
. Experimental section
All chemicals were commercial reagent grades and purchased
from Merck and Aldrich. Chloromethylated polystyrene (CM PS)
resin cross-linked with 1% DVB (70e90 mesh, 1.5e2.0 mmol/g of Cl)
was purchased from Aldrich. XPS (X-ray photoelectron spectros-
copy) data was recorded with 8025-BesTec twin anode XR3E2 X-ray
source system. Thermogravimetric-diffraction thermal analysis
All compounds were characterized by IR, 1H and 13C NMR
spectroscopy.
17
4.3.1. 1-Benzyl-4-phenyl-1H-1,2,3-triazole (5a). White solid; mp
ꢁ
1
(
TG-DTA) was carried out using a thermal gravimetric analysis in-
129e130 C; H NMR (300 MHz, CDCl ):
d
¼7.81 (d, J¼8.5 Hz, 2H),
3
13
strument (NETZSCH TG 209 F1 Iris) with a heating rate of
7.69 (s, 1H), 7.28e7.42 (m, 8H), 5.54 (s, 2H); C NMR (75 MHz,
CDCl ):
¼148.2, 134.7, 130.5, 129.2, 128.84, 128.77, 128.2, 128.1,
125.7, 119.7, 54.2; Calculated for C
N¼17.86%: Found C¼76.48%, H¼5.42%, N¼17.86%.
ꢁ
ꢀ1
1
0 C min . XRD patterns were recorded by an Xpert MPD, X-ray
d
3
1
13
diffractometer using Cu K
a
radiation. H NMR (300 MHz) and
C
15 13 3
H N
C¼76.57%, H¼5.57%,
NMR (75 MHz) spectra were recorded using a Bruker AQS-300
Avance spectrometer. The scanning electron microscopy (SEM)
images were obtained using a scanning electron microscope
VEGAyyTESCAN-LMU. FT-IR spectra were recorded on ABB
Bomem model FTLA 2000 instrument. The Cu content of the
complex was determined using inductively coupled plasma (ICP,
Varian vista-mpx), and surface morphology of the catalyst was
analyzed using Energy-dispersive-X-ray (VEGA, TESCAN-LMU)
equipped with EDX facility. Micro analytical data was collected by
a PerkineElmer, USA, 2400C elemental analyzer.
4.3.2. 1-(4-Nitrobenzyl)-4-phenyl-1H-1,2,3-triazole (5b).44 White
ꢁ
1
solid; mp 158e161 C; H NMR (300 MHz, CDCl ):
3
d
¼8.25 (d,
J¼8.7 Hz, 2H), 7.82 (d, J¼7.5 Hz, 2H), 7.76 (s, 1H), 7.33e7.47 (m, 5H),
1
3
5.71 (s, 2H); C NMR (75 MHz, CDCl ):
3
d
¼148.7, 148.1, 141.7, 130.1,
128.9, 128.54, 128.5, 125.7, 124.4, 119.7, 53.2; Calculated for
C15H12N O C¼64.28%, H¼4.32%, N¼19.99%: Found C¼64.37%,
4 2
H¼4.28%, N¼19.92%.
1
7
4
.3.3. 1-Cyclohexyl-4-phenyl-1H-1,2,3-triazole (5c). White solid;
ꢁ
1
4
.1. Preparation of the polymer-anchored PSeC22eCuI (2)
In a 100 mL round-bottom flask equipped with a magnetic
mp 104e106 C; H NMR (300 MHz, CDCl
H), 7.77 (s, 1H), 7.42 (t, J¼7.3 Hz, 2H), 7.27e7.35 (m, 1H), 4.45e4.55
(m, 1H), 2.26 (d, J¼7.6 Hz, 2H), 1.97 (d, J¼6.0 Hz, 2H), 1.77e1.82 (m,
3
):
d
¼7.83 (d, J¼8.1 Hz,
2
13
stirrer bar, chloromethylated polystyrene resin (2 g, almost
.75 mmol/g of Cl) was allowed to swell in diethyl ether (40 mL) for
4 h; then cryptand-22 (0.65 g, 2.5 mmol) was added to the flask
3H), 1.32e1.52 (m, 3H); C NMR (75 MHz, CDCl
128.8, 127.9, 125.6, 117.3, 60.1, 33.6, 25.20, 25.16; Calculated for
C¼73.98%, H¼7.53%, N¼18.45%: Found C¼73.82%,
H¼7.49%, N¼18.43%.
3
):
d
¼147.3, 130.9,
1
2
14 17 3
C H N
and stirred for 72 h at room temperature. The polymer beads were
filtered and the residue was washed sequentially with diethyl ether
11
(
4ꢃ40 mL), and then dried in an oven to obtain the polymer-
4.3.4. 1-Adamantyl-4-phenyl-1H-1,2,3-triazole (5d). White solid;
ꢁ
1
supported cryptand-22 (1).
mp 218e222 C; H NMR (300 MHz, CDCl
3
):
d
¼7.80 (d, J¼8.2 Hz,
Then, the C22-functionalized polymer (1) was swollen in EtOH
2H), 7.67 (s, 1H), 7.40 (t, J¼8.0 Hz, 2H), 7.27e7.33 (m, 1H), 2.36 (s,
13
(
50 mL) for 1 h; then, CuI (0.42 g, 2.2 mmol) was added and the
6H), 2.10 (s, 3H), 1.73 (s, 6H); C NMR (75 MHz, CDCl ):
3
d
¼148.3,
mixture was heated at reflux in that solvent for 24 h in N
2
130.5, 128.2, 128.1, 125.7, 119.5, 66.9, 49.3, 35.5, 32.6; Calculated for