Copper nanoparticles on charcoal for multicomponent catalytic synthesis of 1,2,3-triazole derivatives from benzyl halides or alkyl halides, terminal alkynes and sodium azide in water as a "green" solvent

Article abstract of DOI:10.1002/adsc.200800612

A one-pot procedure for synthesis of 1,2,3-triazole derivatives via the three-component coupling (TCC) reaction between terminal alkynes, benzyl or alkyl halides, and sodium azide in the presences of 1 mol% nanoparticles copper/carbon (Cu/C) catalyst has

Full text of DOI:10.1002/adsc.200800612

FULL PAPERS
DOI: 10.1002/adsc.200800612
Copper Nanoparticles on Charcoal for Multicomponent Catalytic
Synthesis of 1,2,3-Triazole Derivatives from Benzyl Halides or
Alkyl Halides, Terminal Alkynes and Sodium Azide in Water as a
“Green” Solvent
Hashem Sharghi,a,* Reza Khalifeh,a and Mohammad Mahdi Doroodmanda
a
Department of Chemistry, Shiraz University, Shiraz 71454, Iran
Fax : (+98)-711-228-0926; phone: (+98)-711-228-4822; e-mail: shashem@chem.susc.ac.ir
Received: October 8, 2008; Revised: December 14, 2008; Published online: January 12, 2009
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200800612.
Abstract: A one-pot procedure for synthesis of 1,2,3- practical for the synthesis of new azacrown ether and
triazole derivatives via the three-component coupling anthraquinone derivatives of triazole. The heteroge-
(TCC) reaction between terminal alkynes, benzyl or neous catalysts were fully characterized by scanning
alkyl halides, and sodium azide in the presences of electron microscopy (SEM), atomic forced microsco-
1 mol% nanoparticles copper/carbon (Cu/C) catalyst py (AFM), X-ray diffraction (XRD), inductively
has been developed. The catalyst showed high cata- coupled plasma (ICP) analysis and FT-IR experi-
lytic activity and 1,4-regioselectivity for the [3+ mental techniques. The catalyst was recycled ten
2]Huisgen cycloaddition in water as a “green” sol- times without significant loss of activity.
vent and good to excellent yields were obtained in
all cases. This procedure eliminates the need to Keywords: activated carbon; anthraquinone deriva-
handle organic azides, and they are generated in situ. tives; aza crown ethers; heterogeneous catalysts;
The reaction has a broad scope and is especially 1,2,3-triazoles; water
Introduction
dynamic instability and the formation of undesired
alkyne-alkyne coupling products is sometimes ob-
1,2,3-Triazoles are an important class of heterocyclic served in their presence.[9] Nevertheless, nitrogen- or
compounds due to their wide range of applications in- phosphorus-based ligands have been shown to protect
cluding use as pharmaceutical agents, agrochemicals, the metal center from oxidation and disproportiona-
industrial applications such as dyes, corrosion inhibi- tion, while enhancing its catalytic activity.[10] To im-
tion (of copper and copper alloys), photostabilizers, prove the recovery and reuse, copper species have
and photographic materials.[1]
been immobilized onto various supports such as acti-
The most popular method for the construction of vated carbon,[11] amine-functionalized polymers,[12]
the 1,2,3-triazole framework is the 1,3-dipolar Huis- zeolites[13] , amine-functionalized silica[14] and alumi-
gen cycloaddition reaction of azides with alkynes.[2] num oxyhydroxide fiber.[15] Although organic azides
The Cu(I)-catalyzed azide-alkyne cycloaddition are generally stable against most reaction conditions
(CuAAC),[3] one of the most reliable “click reac- such as water and oxygen,[16] isolation or purification
tions”,[4] has enabled the practical and efficient prepa- of lower organic azides or polyazides can be problem-
ration of 1,4-disubstituted-1,2,3-triazoles, from a wide atic. Therefore, a procedure that avoids the isolation
range of substrates with excellent selectivity, which of organic azides is desirable. Recently some exam-
cannot be prepared via traditional Huisgen uncata- ples were reported for the in situ generation of organ-
lyzed thermal approaches.[5] Active copper(I) catalytic ic azides using a one-pot procedure to prepare 1,2,3-
species can be prepared in situ by reduction of cop- triazole derivatives based on the three-component
per(II) salts,[3a] oxidation of copper(0) metal,[6] or cop- coupling reaction.[14,17] As a part of our continued ef-
per(II)/copper(0) comproportionation.[7] Copper(I) forts to utilize heterogeneous catalysts for developing
salts have been less used[3b,8] because of their thermo- organic reactions,[18] herein we report on a new and
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reused catalyst system based on Cu(I) on charcoal
(Cu/C). This heterogeneous catalyst system exhibits
an excellent catalytic performance for 1,3-dipolar
Huisgen cycloaddition reaction for the construction of
the 1,2,3-triazole framework. Moreover, Cu/C can be
repeatedly used for this transformation and subse-
quently recovered after the reaction.
Results and Discussion
The copper catalyst immobilized on activated carbon
was readily prepared in a two-step procedure. In a
general procedure, the activated carbon was refluxed
with a nitric acid solution for several hours and
washed with deionized water until pH 6–7 and then
dried in an oven at 1108C overnight under vacuum.[19]
The oxidized activated carbon was refluxed with a so-
lution of CuI under an N2 atmosphere in absolute
Figure 1. SEM image of copper particles on activated
carbon as substrate.
EtOH for the synthesis of CuI/Cu nanostructures. tals of CuI to form nanocrystals of deposited CuI.
This method was developed for the effective synthesis The yellowness of the solution durinÀg the reflux is
of copper nanoparticles incorporated heterogeneously good evidence for the formation of I3 based on fol-
as catalyst in some organic reactions. The CuI/Cu lowing equation:
nanostructures were then chemically incorporated
into activated carbon via p-bonds. This interaction is
the result of the back-donation of d electrons from
the occupied 4d orbital of the copper ion to the unoc-
cupied p*-2p antibonding orbitals of the carbon-
The above reactions are repeated continuously
carbon double bond.[20] Scanning electron microscopy during several steps of the use of Cu/C that make it
(SEM), atomic forced microscopy (AFM), X-ray dif- active in playing the catalytic role of Cu/CuI (the
fraction (XRD) analysis and FT-IR experimental nature of the copper catalyst) in organic reactions.
techniques were used to characterize the CuI/Cu
The size and morphology of the copper nanoparti-
nanostructures. According to the conditions of the re- cles are clearly observed based on two-dimensional
action, the following equations are proposed for CuI (2-D), three-dimensional (3-D) AFM images
in ethanol:[27]
(Figure 2). The AFM images of copper nanoparticles
reveal the spherical copper nanoparticles and CuI
nanocrystals which are normally distributed on acti-
vated carbon. The average size of the copper nano-
structures is estimated to 80–300 nm according to the
voltage profile of AFM image (Figure 2c). According
Because of the low solubility of CuI in ethanol (Ksp to the histogram based on the AFM image (Fig-
in water=5.1 E 12), most of the copper iodide crys- ure 2d), the maximum frequency percent of copper
tals tend to deposit on to the activated carbon. The nanoparticles has been estimated to by around
CuI crystals are graphically observed using SEM 250 nm.
(Figure 1). Based on the SEM image, CuI crystals are
estimated to around several micrometers in size.
Figure 3 shows the XRD patterns of capped copper
nanoparticles on activated carbon. The peak positions
Anyway, the poor solubility of the CuI under the are consistent with metallic copper and copper iodide
condition of the reaction causes the formation of a nanocrystals. Sharp peaks of copper are observed
dilute solution of Cu+. Then, via a disproportionation which indicate the crystalline nature of the products.
reaction, Cu+ is changed to Cu nanoparticles and Planes of charcoal, CuI nanocrystals and Cu nanopar-
Cu2+ species according to the following equation:
ticles are reported in Table 1. The diffraction features
were consistent with the “fcc” crystal structures of
copper and copper iodide.[22] The size of the copper
nanoparticle was also determined from X-ray line
broading using the Debye–Scherrer formula[23] given
Then Cu 2+ as the product of the disproportionation as D=0.9 l/b cosq, where D is the average crystalline
reaction of Cu+, reacts with iodide ion or micro crys- size, l the X-ray wavelength used, b the angular line
208
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Figure 2. AFM images of copper nanoparticles, a: 2-D, b: 3-D, c: voltage profile and d: the histogram representing the aver-
age size of copper nanoparticles.
width at half maximum intensity and q the Braggꢁs
To evaluate the Cu content, the supported catalyst
angle. For q=208, l=1.056 ꢂ and b=0.36 mm, the was treated with concentrated HCl and concentrated
average size of the copper nanoparticles on activated nitric acid to digest the copper species and then ana-
carbon is estimated to be around 283.3 nm.
lyzed by inductively coupled plasma (ICP) analysis.
Comparison between the FT-IR spectra of the The Cu content was determined to be 9.97% w/w
copper nanoparticles on activated carbon with that of (See Experimental Section for details).
activated carbon, reveals weak absorption band at
The principle advantages of this immobilization
around 667 cmÀ1 (Figure 4). This is related to the im- technique include the absence of any complexity in
mobilization of copper nanoparticles on activated the immobilization process, the widespread availabili-
carbon. Also the shift observed in the peak absorp- ty of activated carbon, the lack of any laborious need
tion of the carbonyl group from 1635.5 to 1612 cmÀ1 is to alter the catalyst to facilitate the immobilization,
related to the chemical bond formed between the car- the rapidity and experimental simplicity of the proce-
boxylic group and Cu+.[24c] This decrease in the elec- dure by which the immobilization can be completed.
tron density at the carbonyl group is probably due to
To exploit a method for the preparation of new
the donation of electrons from the carbonyl group 1,2,3-triazole derivatives, the reaction of benzyl bro-
into Cu+.
mide, phenylacetylene and sodium azide in the pres-
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Figure 3. XRD pattern of copper nanoparticles on activated carbon as substrate.
ence of Cu/C via a 1,3-dipolar Huisgen cycloaddition lated yield, and selectivity. Water clearly stands out as
reaction was chosen as a model and its behavior was the solvent of choice with its fast reaction rate, high
studied under a variety of conditions via TLC and yield, selectivity, cheapness, “green” solvent nature
NMR spectroscopy (Table 2).
and environmental acceptability. The reaction be-
During our optimization studies, various solvents tween, benzyl bromide, phenylacetylene and sodium
were examined and it was found that the solvent azide in the presence of 1 mol% of Cu/C in the water,
plays a significant role in terms of reaction rate, iso- furnished the 1,4-disubstituted triazole product in
91% yield after stirring for 45 min at 1008C in a un-
capped vial (Scheme 1). The product was isolated by
simple washing of the solid mass by acetone followed
by the usual work-up. An increase in the amount of
Cu/C had negligible effects on the efficiency of the re-
action.
Table 1. Analysis of XRD patterns related to CuI/Cu on ac-
tivated carbon.
2-Theta-Scale (2q)
Matrix and Morphology
Reference
C
Cu
CuI/CuI3
Structural assignments of triazole 1 were made by
comparison of the 1H- and 13C NMR spectra with
25.5
29.5
40
N
–
–
A
G
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
1
those reported previously. In particular, the H NMR
spectra show resonances of the proton in the 5-posi-
tion of the 1,2,3-triazole ring that perfectly agree with
literature data.[17c]
To investigate the generality and versatility of this
method, the reaction was extended to various struc-
turally diverse terminal alkynes and alkyl halides. In
all cases, [3+2]cycloadditions were complete in a rea-
50.2
52.1
61.2
67.2
69.2
77
G
G
N
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
[22]
[22]
ACHTUNGTRENN[UNG 22,24c]
210
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Table 2. 1,3-Dipolar Huisgen cycloaddition reaction of benzyl bromide, phenylacetylene and sodium azide under various con-
ditions.
Entry
Catalyst
Conditions
Temperature [8C]
Time
Yield [%]
1
2
3
4
5
6
7
8
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (1 mol%)
Cu/C (5 mol%)
neat
Dioxane
THF
100
100
65
2 h
6 h
6 h
2 h
1 h
1.5 h
2 h
2 h
2 h
0
15
20
35
58
45
40
65
40
50
40
91
92
t-BuOH
EtOH (96%)
CH3CN
DMF
H2O/dioxane
H2O/THF
H2O/DMF
H2O
80
reflux
reflux
100
100
65
100
25
100
100
9
10
11
12
13
2 h
24 h
45 min
40 min
H2O
H2O
substituents were subjected to the same reaction con-
ditions as 3 to furnish the corresponding 1,2,3-triazole
derivatives. However the rate drops as electron-with-
drawing substituents are added, as in 4 (Table 3,
entry 5).
We envisaged that the reaction of anthraquinone
derivatives[25] (5 and 7) containing a single bromo-
methyl group with sodium azide would lead to the
quantitative formation of the desired azidomethyl
group, which could then be coupled with phenylacety-
lene to give the next-generation 1,2,3-triazole deriva-
tives in good yields.(Table 3, entries 6 and 7). We felt
that this methodology could then be extended to syn-
thesize azacrown ether-containing triazoles. The aza-
crown ether, which has a chloroacetylated substituent
at the nitrogen position (9), gave the corresponding
triazole 10 in good yield (Table 3, entry 8). Azacrown
ether propargylamine 11 also reacted without any
problems to give the corresponding triazole 12 in high
yield (Table 3, entry 9). We decided to extend the
scope of this methodology to the anthraquinone di-
propargyl ether 13 as starting material; the reaction
proceeded smoothly in good yield.
Figure 4. FT-IR spectra of a: activated carbon, b: activated
carbon supported with Cu nanoparticles.
The reaction of an alkylacetylene such as 1-hexyne
sonable time and 1,2,3-triazole derivatives were isolat- and aliphatic terminal alkynes bearing functional
ed in good to high yields. groups afforded the desired triazoles (15, 16 and 17)
The use of this methodology in the reaction of the in high yields, although prolonged reaction times
sodium azide, alkyl or benzyl halides with different were required (Table 3, entries 11–13). When methyl
terminal alkynes produced only one of the possible iodide and allyl bromide were used as substrate, the
regioisomers, as expected (Table 3). Various benzyl reaction was performed in a sealed tube to afford the
halides with both electron-donating and -withdrawing desired product in good yield. The use of methylene
Scheme 1.
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Table 3. The reaction of alkyl and benzyl halide (1 mmol), terminal alkyne (1 mmol) and sodium azide (1.1 mmol) catalyzed
by Cu/C (1 mol%) in water at 1008C.
Entry
Halide
Alkyne
Product
Time Yield
[h]
[%]
1
2
3
4
5
1
0.6
91
1
90
87
88
84
2
3
4
1.5
0.5
2.5
6
7
5
7
6
8
5
6
78
75
8
9
9
10
12
6
4
79
75
11
13
10
14
8
72
11
12
15
16
2.5
3
76
81
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Table 3. (Continued)
Entry
Halide
Alkyne
Product
Time Yield
[h]
[%]
13
17
3
84
14
15
16
18
19
20
10
8
86
83
71
12
17
18
21
22
20
18
69
85
23
19
20
24
no reaction
24
1
–
89
iodide as an alkyl halide afforded the bridged 1,2,3- benzyl bromide, phenylacetylene and sodium azide on
triazole 20 in 71% yield (Table 3, entry 16). Next, we a 100-mmol scale in the presence of the heterogene-
explored the synthesis of symmetrical bis-triazoles ous catalyst (Table 3, entry 20). As expected, the reac-
starting from the bis-OTs derivative 22, by the succes- tion proceeded similar to the case on a smaller scale
sive 1,3-dipolar cycloaddition reactions with phenyl- (Table 3, entry 1), and the desired 1,2,3-triazole was
ACHTUNGTRENNUNG
In an attempt to broaden the scope of our method- dition of phenylacetylene, benzyl bromide and
ology, the possibility of performing the reaction with sodium azide. The charcoal-supported CuI was recov-
an alkyl halide instead of benzyl halide was also in- ered simply by filtration after each experiment, after
vestigated. In this way, 2-phenylethyl bromide was re- washing with acetone and drying in the air it could be
acted with phenylacetylene and sodium azide in the reused directly without further purification for the
presence of Cu/C at 1008C for 18 h to afford the ex- 1,2,3-triazole synthesis in more than 10 successive re-
pected product in 85% yield.
No competitive formation of N H triazoles, result- Cu/C was found to contain 9.83% (w/w) of Cu based
ing from the addition of an inorganic azide to the on ICP analysis, which is comparable to the initial
actions. After 10 consecutive reactions, the recovered
À
alkyne, was detected with this catalytic system.
value of 9.97% (w/w), indicative of less than 1.40%
As expected, internal alkynes gave no reaction. The leaching during the reaction cycles (see Experimental
reactive behavior is in agreement with a mechanism Section for details). The stability of copper species on
involving the formation of a CuI acetylide species, activated carbon is so high that, no leaching was ob-
probably on the Cu/C surface (Table 3, entry 19).
served even in the presence of copper complexing
To access the feasibility of applying this method in agents such as azacrown ethers.[27a]
a preparative scale, we carried out the reaction of
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until pH 6–7 and then dried in an oven at 1108C overnight
Also, the FT-IR spectrum and the XRD pattern of
the copper catalyst supported on activated carbon, an-
alyzed after its use as catalyst in organic reactions for
at least 10 times, were similar to those obtained
before the first cycle.[26]
under vacuum.[19]
Deposition of Copper on Purified Activated Carbon
using CuI as Copper Source
In conclusion, we have developed a simple and re-
producible synthetic method for a recyclable hetero-
geneous copper catalyst (Cu/C). We have determined
the morphology, the surface and total composition of
the mixed Cu/C by SEM, AFM, XRD, IR and ICP
analyses. The Cu/C surface is mostly composed of
both CuI and Cu nanoparticles. With this catalyst, a
safe and efficient three-component reaction for the
regioselective generation of 1,4-disubstituted 1,2,3-tri-
azoles has been developed. The method avoids isola-
tion and handling of potentially unstable small organ-
ic azides and provides the triazole products in pure
form. The scope of the cycloaddition using our cata-
lyst is quite broad; various terminal alkynes react
readily with benzyl and alkyl halides at 1008C in
water. Furthermore, the Cu/C can be recovered and
recycled by simple filtration of the reaction solution
and reused for at least ten consecutive trials without
decrease in the activity.
CuI (100 mg) was dissolved in 30 mL absolute ethanol, and
magnetically stirred in a pre-heated oil bath at reflux tem-
perature for 4 h under a nitrogen atmosphere in the pres-
ence of 1.0 g of purified activated carbon. The resulting ma-
terials were washed with ethanol (4ꢄ30 mL); no leaching of
the copper was observed. Finally, the copper in charcoal was
dried under vacuum in an oven overnight at 1108C. To eval-
uate the copper content, the supported copper was treated
with concentrated HCl and HNO3 (1:1) followed by ICP
analysis. The copper content was determined to be 9.97%
w/w.
Determination of the Copper Content in Cu/C
Catalyst
The Cu/C (100 mg) was extracted with concentrated HCl
(5ꢄ2 mL) in a screw-capped vessel, followed by treatment
with concentrated nitric acid (2 mL) to digest the metal
complex. The mixture was then transferred into a volumetric
flask (100 mL), diluted 1:50 for the second time and was an-
alyzed by the ICP analysis. The copper concentration was
determined from the atomic emissions (324.754 nm) by ref-
erence to a linear (R=0.99) calibration curve of (1–4 ppm)
of CuI prepared in a manner identical to the sample prepa-
ration.
Experimental Section
Instrumentation, Analyses and Starting Material
General Procedure
NMR spectra were recorded on a Bruker Avance DPX-250
(1H NMR at 250 MHz and 13C NMR at 62.9 MHz) spec-
trometer in pure deuterated solvents with tetramethylsilane
as an internal standard. IR spectra were obtained using a
Shimadzu FT-IR 8300 spectrophotometer. Scanning electron
micrographs were obtained with the SEM instrumentation
XL-30 FEG SEM (Philips, at 20 KV). An atomic forced mi-
croscope (AFM, DME-SPM, version 2.0.0.9) was also used
for AFM images. Mass spectra were determined on a Shi-
madzu GCMS-QP 1000 EX instruments at 70 or 20 eV.
Melting points determined in open capillary tubes in a
Bꢃchi-535 circulating oil melting point apparatus. X-ray dif-
fraction (XRD, D8, Advance, Bruker, axs) patterns were ob-
tained for characterization of the heterogeneous catalyst.
The ICP analysis data were obtained using a Varian Vista-
pro analyzer. The purity determination of the substrates and
reaction monitoring were accomplished by TLC on silica gel
PolyGram SILG/UV 254 plates. Column chromatography
was carried out on short columns of silica gel 60 (70–230
mesh) in glass columns (2–3 cm diameter) using 15–30 g of
silica gel per g crude mixture. Chemical materials were pur-
chased from Fluka, Aldrich and Merck. The used activated
carbon was also purchased from Merck (Atr. No. 9631, 0.3–
0.05 mm).
The Cu/C catalyst was subjected to 10 successive reuses
under the reaction conditions: For each reaction, alkyl
halide (1 mmol), alkyne (1 mmol) and sodium azide
(1.1 mmol) were stirred in water (1 mL) in the presence of
the heterogeneous catalyst (1 mol%, 0.021 g) at 1008C in a
uncapped vial. According to the ICP analysis, the copper
content in the heterogeneous catalyst was determined to be
9.97% (w/w). Therefore, each gram of heterogeneous cata-
lyst includes 0.525 mmol of copper. For 1 mmol of reactants,
0.01 mmol of catalyst is needed, which is equal to 0.021 g of
the heterogeneous catalyst. The reaction was complete after
appropriate time (Table 3) as monitored by TLC analysis.
After the reaction was complete the whole reaction mixture
was directly passed through celite and rinsed with acetone
(3ꢄ15 mL). The recovered catalyst was dried and stored for
another consecutive reaction run. The acetone was removed
by rotation evaporator under vacuum and the residue was
precipitated in water. The precipitate was collected by filtra-
tion. After washing with water three times, the precipitate
was dried under vacuum for 24 h at room temperature,
which resulted in a 91% yield as white solid. For further pu-
rification the solid was recrystallized with ethanol/water
(3:1).
1-Benzyl-4-phenyl-1H-1,2,3-triazole (1): Recrystallization
from EtOH/H2O (3:1) gave compound 1 as colorless crystals
in 91% yield; mp 129–129.58C; IR (KBr): n=694 (s), 729
(s), 768 (s), 1049 (m), 1076 (m), 1223 (m), 1358 (w), 1466
Activated Charcoal Oxidation
1
The activated carbon was refluxed with a 5.0M nitric acid
solution for 6 h (1.0 g/30 mL), washed with deionized water
(m), 3121 (w) cmÀ1; H NMR (CDCl3, 250 MHz): d=5.53 (s,
2H), 7.26–7.41 (m, 6H), 7.69 (s, 1H), 7.79–7.82 (m, 4H);
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13C NMR (CDCl3, 62.9 MHz): d=54.1, 119.7, 125.7, 128.0,
128.2, 128.7, 128.8, 129.1, 130.6, 134.7, 148.1; MS: m/z (%)=
237 (M+ +2, 0.2), 236 (M+ +1, 7.3), 235 (M+, 7.7), 207
(24.7), 206 (30.8), 179 (9.7), 149 (23.1), 116 (94.8), 91 (100),
57 (56.0); anal. calcd. for C15H13N3 (235.284): C 76.57, H
5.57: found: C 76.40, H 5.69.
(54.2), 55 (100); anal. calcd. for C23H15N3O3 (381.384): C
72.43, H 3.96; found: C 72.58, H 4.12.
1-Methoxy-2-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]an-
thra-9,10-quinone (8): Recrystallization from EtOH/H2O
(3:1) gave compound 8 as a yellow powder in 75% yield;
mp 211–2128C; IR (KBr): n=694 (m), 714 (s), 764 (m), 964
(m), 1014 (s), 1045 (s), 1265 (s), 1323 (s), 1574 (m), 1670
1-(4-Bromobenzyl)-4-phenyl-1H-1,2,3-triazole (2): Recrys-
tallization from EtOH/H2O (3:1) gave compound 2 as color-
less crystals in 87% yield; mp 152–152.58C; IR (KBr): n=
690 (s), 764 (s), 798 (s), 1049 (m), 1076 (s), 1219 (s), 1350
(vs), 3078 (m) cmÀ1 1H NMR (DMSO-d6, 250 MHz): d=
;
3.85 (s, 3H), 5.80 (s, 2H), 7.29 (d, 1H, J=7.1 Hz), 7.41 (t,
1H, J=7.3 Hz), 7.64 (d, 1H, J=7.9 Hz), 7.83–7.90 (m, 5H),
7.98 (d, 1H, J=7.9 Hz), 8.10 (t, 1H, J=7.3 Hz), 8.65 (s,
1H); 13C NMR (DMSO-d6, 62.9 MHz): d=48.7, 62.4, 122.6,
123.4, 125.6, 126.3, 127.2, 128.4, 129.3, 131.0, 132.4, 134.4,
134.7, 135.0, 135.5, 135.6, 137.6, 147.0, 158.7, 181.8, 182.5;
MS: m/z (%)=397 (M+ +2, 1.6), 396 (M+ +1, 6.7), 395 (M+,
2.9), 369 (7.9), 353 (6.2), 337 (13.3), 264 (11.9), 252 (24.2),
221 (10.6), 165 (16.2), 116 (100), 83 (24.9), 57 (48.5); anal.
calcd. for C24H17N3O3 (395.410): C 72.90, H 4.33; found: C
72.79, H 4.17.
1
(w), 1435 (m), 1462 (m), 1485 (s), 3082 (m) cmÀ1; H NMR
(CDCl3, 250 MHz): d=5.52 (s, 2H), 7.17 (d, 2H, J=8.4 Hz),
7.24–7.44 (m, 3H), 7.51 (d, 2H, J=8.4 Hz), 7.67 (s, 1H),
7.80 (d, 2H, J=8.4 Hz); 13C NMR (CDCl3, 62.9 MHz): d=
53.4, 119.7, 122.8, 125.7, 127.6, 128.3, 128.7, 129.1, 129.6,
132.2, 133.8, 148.3; MS: m/z (%)=316 (M+ +2, 1.8), 315
(M+ +1, 1.8), 314 (M+, 2.4), 312 (0.8), 284 (4.7), 286 (5.3),
207 (8.6), 180 (2.5), 178 (2.7), 171 (15.1), 169 (16.3), 116
(100), 89 (37.3); anal. calcd. for C15H12BrN3 (314.180): C
57.34, H 3.85; found: C 57.17, H 3.98.
7-[(4-Phenyl-1H-1,2,3-triazol-1-yl)acetyl]-5,6,7,8,9,10-hex-
ahydro-2H-1,13,4,7,10-benzodioxatriazacyclopentadecine-
3,11ACTHNURGTNE(GNU 4H,12H)-dione(10): Recrystallization from EtOH/H2O
1-(4-Methylbenzyl)-4-phenyl-1H-1,2,3-triazole (3): Recrys-
tallization from EtOH/H2O (3:1) gave compound 3 as color-
less crystals in 88% yield; mp 1108C; IR (KBr): n=694 (s),
764 (s), 1045 (m), 1076 (m), 1223 (s), 1350 (m), 1462 (m),
(3:1) gave compound 10 as a white powder in 79% yield;
mp 2078C; IR (KBr): n=768 (w), 1045 (w), 1122 (w), 1238
(m), 1500 (s), 1539 (s), 1666 (vs), 2928 (w), 3302 (m), 3391
1516 (m), 3117 (w), 3445 (br) cmÀ1 1H NMR (CDCl3,
;
(s) cmÀ1 1H NMR (CDCl3, 250 MHz): d=3.46–3.86 (m,
;
250 MHz): d=2.36 (s, 3H), 5.52 (s, 2H), 7.30–7.43 (m, 7H),
7.64 (s, 1H), 7.79 (dd, 2H, J1 =8.1, J2 =1.5 Hz); 13C NMR
(CDCl3, 62.9 MHz): d=21.2, 53.9, 119.6, 126.0, 128.1, 128.8,
130.2, 130.6, 131.7, 138.6, 148.1; MS: m/z (%)=251 (M+ +2,
3.0), 25 0(M++1, 15.9), 249 (M+, 16.2), 220 (41.4), 206
(14.2), 179 (16.3), 130 (7.0), 116 (100), 89 (25.9), 77 (27.4);
anal. calcd for C16H15N3 (249.311): C 77.08, H 6.06; found: C
76.92, H 5.94.
8H), 4.52 (s, 2H), 4.75 (s, 2H), 5.21 (s, 2H), 6.95–7.06 (m,
4H), 7.30–7.41 (m, 3H), 7.71–7.76 (m, 2H), 7.87 (s, 1H),
7.23 (s, 2H); 13C NMR (CDCl3, 62.9 MHz): d=48.6, 51.0,
115.4, 118.3, 121.7, 124.0, 125.7, 128.1, 128.7, 130.4, 147.9,
167.5129.1, 136.1, 143.5, 146.3, 167.5; MS: m/z (%)=479
(M+ +1, 2.5), 478 (M+, 4.2), 451 (3.2), 450 (2.6), 332 (0.2),
304 (0.4), 293 (0.4), 292 (0.5), 277 (2.5), 225 (2.1), 206 (6.3),
194 (3.7), 167 (4.2), 130 (24.3), 103 (34.7), 85 (51.1), 56
(100); anal. calcd. for C24H26N6O5 (478.501): C 60.24, H
5.48; found: C 60.07, H 5.62.
1-(4-Nitrobenzyl)-4-phenyl-1H-1,2,3-triazole (4): Recrys-
tallization from EtOH/H2O (3:1) gave compound 4 as pale
yellow crystals in 84% yield; mp 156–1578C; IR (KBr): n=
690 (s), 733 (s), 764 (s), 1045 (m), 1076 (m), 1223 (m), 1350
(s), 1520 (s), 1605 (m), 3082 (m) cmÀ1 1H NMR (CDCl3,
;
7-(2-Propynyl)-5,6,7,8,9,10-hexahydro-2H-1,13,4,7,10-
benzodioxatriazacyclopentadecine-3,11ACTHNUTRGENUG(N 4H,12H)-
250 MHz): d=5.68 (s, 2H), 7.32–7.38 (m, 3H), 7.42 (d, 2H,
J=8.5 Hz), 7.78 (s, 1H), 7.79 (d, 2H, J=7.9 Hz), 8.19 (dd, dione (11)
2H, J1 =9.1, J2 =2.2 Hz); 13C NMR (CDCl3, 62.9 MHz): d=
A mixture of azacrown ether[27] (5 mmol), propargyl bro-
mide (10 mmol), and K2CO3 (12 mmol) in DMF (50 mL)
was stirred at room temperature for 24 h and then poured
into ice/water (500 mL). The mixture was filtered under
vacuue and the residue was air-dried to constant weight to
give 11 in 95% yield; mp 1108C; IR (KBr): n=744 (s), 818
(m), 1057 (s), 1134 (s), 1223 (s), 1261 (s), 1439 (m), 1462
53.1, 119.8, 124.3, 125.7, 128.5, 128.9, 130.1, 141.8, 148.6;
MS: m/z (%)=281 (M+ +1, 4.1), 280 (M+, 5.6), 252 (3.3),
206 (7.0), 136 (5.0), 116 (100.0), 89 (41.0), 63 (18.8); anal.
calcd. for C15H12N4O2 (280.282): C 64.28, H 4.32; found: C
64.09, H, 4.45.
1-Hydroxy-2-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]an-
thra-9,10-quinone (6): Recrystallization from EtOH/H2O
(3:1) gave compound 6 as an orange powder in 78% yield;
mp 2098C; IR (KBr): n=694 (s), 714 (s), 764 (s), 999 (s),
1045 (w), 1284 (s), 1257 (s), 1350 (s), 1427 (s), 1589 (s), 1632
(m), 1512 (s), 1682 (vs), 2847 (m), 3229 (m), 3406(s) cmÀ1
;
1H NMR (CDCl3, 250 MHz): d=2.26 (s, 1H), 2.85 (t, 4H,
J=5.3 Hz), 3.32 (s, 2H), 3.37 (t, 4H, J=5.3 Hz), 4.46 (s,
4H), 6.82–7.01 (m, 4H), 7.42 (s, 2H); 13C NMR (CDCl3,
62.9 MHz): d=35.0, 37.1, 51.3, 66.8, 74.6, 75.4, 112.3, 121.9,
146.5, 167.1; MS: m/z (%)=333 (M+ +2, 6.6), 332 (M+ +1,
35.2), 331 (M+, 23.4), 293 (1.4), 292 (2.2), 207 (14.4), 165
(33.6), 123 (33.2), 94 (78.9), 69 (82.3), 55 (100); anal. calcd.
for C17H21N3O4 (331.366): C 61.62, H 6.39; found: C 61.47,
H 6.54.
(s), 1670 (s), 3086 (m) cmÀ1
;
1H NMR (DMSO-d6,
250 MHz): d=5.72 (s, 2H), 7.29 (d, 1H, J=7.0 Hz), 7.40 (t,
1H, J=7.3 Hz), 7.64 (d, 1H, J=7.9 Hz), 7.81–7.85 (m, 5H),
7.90–8.21 (m, 2H), 8.62 (s, 1H), 12.84 (s, 1H); 13C NMR
(DMSO-d6, 62.9 MHz): d=47.6, 115.7, 118.7, 122.0, 125.1,
126.5, 126.8, 127.8, 128.8, 130.3, 130.5, 132.5, 132.8, 134.6,
135.2, 136.6, 146.4, 159.1, 181.3, 188.3; MS: m/z (%)=382
(M+ +1, 5.7), 381 (M+, 5.9), 368 (7.0), 366 (5.6), 314 (17.5),
300 (3.6), 282 (9.4), 263 (3.5), 251 (7.5), 238 (18.8), 209 (9.2),
181 (7.1), 164 (5.0), 145 (21.3), 116 (10.5), 97 (29.1), 71
7-[(1-Benzyl-1H-1,2,3-triazol-4-yl)methyl]-5,6,7,8,9,10-hex-
ahydro-2H-1,13,4,7,10-benzodioxatriazacyclopentadecine-
3,11
ACHTUNGTRENUN(NG 4H,12H)-dione (12): Recrystallization from EtOH/H2O
(3:1) gave compound 12 as a colorless powder in 75% yield;
Adv. Synth. Catal. 2009, 351, 207 – 218
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
215

Hashem Sharghi et al.
1223 (m), 1458 (m), 3263 (br) cmÀ1 1H NMR (CDCl3,
FULL PAPERS
mp 195–1968C; IR (KBr): n=752 (m), 818 (m), 1049 (s),
;
1130 (s), 1219 (s), 1257 (s), 1504 (s), 1527 (s), 1682 (vs), 2858
250 MHz): d=4.65 (s, 2H), 5.40 (s, 2H), 7.17–7.29 (m, 5H),
7.45 (s, 1H); 13C NMR (CDCl3, 62.9 MHz): d=4.0, 55.8,
122.0, 128.1, 128.7, 129.0, 134.6, 148.3; MS: m/z (%)=191
(M+ +2, 0.1), 190 (M+ +1, 0.8), 189 (M+, 1.1), 160 (3.3), 149
(3.4), 143 (5.2), 130 (6.6), 91 (100), 65 (21.5); anal. calcd. for
C10H11N3O (189.214): C 63.48, H 5.86; found: C 63.62, H
5.73.
1
(w), 3229 (m), 3406 (s) cmÀ1; H NMR (CDCl3, 250 MHz):
d=2.77 (t, 4H, J=5.3 Hz), 3.52 (t, 4H, J=5.3 Hz), 3.95 (s,
2H), 4.41 (s, 4H), 5.44 (s, 2H), 6.84–7.05 (m, 4H), 7.13–7.14
(m, 2H), 7.26 (s, 1H), 7.30–7.36 (m, 3H), 7.56 (s, 2H);
13C NMR (CDCl3, 62.9 MHz): d=35.3, 44.3, 52.0, 54.1, 67.1,
112.8, 122.2, 127.8, 128.7, 129.1, 134.5, 143.4, 146.3, 167.2;
MS: m/z (%)=466 (M+ +2, 0.9), 465 (M+ +1, 8.2), 464 (M+,
7.6), 392 (3.7), 293 (6.5), 292 (14.1), 227 (11.1), 215 (12.6),
173 (16.0), 144 (25.7), 121 (10.5), 91 (100), 56 (33.8); anal.
calcd. for C24H28N6O4 (464.517): C 62.06, H 6.08; found: C
61.95, H 6.19.
2-(1-Benzyl-1H-1,2,3-triazol-4-yl)-2-propanol (17): Recrys-
tallization from EtOH/H2O (3:1) gave compound 17 as col-
orless crystals in 84% yield; mp 778C; IR (KBr): n=698
(w), 733 (s), 795 (m), 960 (m), 1057 (m), 1173 (s), 1219 (m),
1369 (m), 1458 (m), 1500 (w), 2978 (s), 3310 (br) cmÀ1
;
1H NMR (CDCl3, 250 MHz): d=1.57 (s, 6H), 3.18 (s, 1H),
5.42 (s, 2H), 7.21–7.36 (m, 5H), 7.39 (s, 1H); 13C NMR
(CDCl3, 62.9 MHz): d=30.4, 54.1, 68.4, 119.2, 128.1, 128.7,
129.1, 134.6, 152.1; MS: m/z (%)=217 (M+, 0.5), 204 (0.4),
203 (2.3), 202 (16.0), 201 (3.2), 130 (1.6), 91 (100), 90 (30.3),
65 (18.5); anal. calcd. for C12H15N3O (217.267): C 66.34, H
6.96; found: C 66.49, H 7.11.
1,8-Bis(2-propynyloxy)anthra-9,10-quinone (13)
A mixture of 1,8-dihydroxyanthraquinone (5 mmol), prop-
argyl bromide (20 mmol), and K2CO3 (24 mmol) in DMF
(50 mL) was stirred at room temperature for 24 h and then
poured into ice/water (500 mL). The mixture was filtered
under vacuum and the residue was air-dried. The crude
product was purified by column chromatography on silica
gel using n-hexane as eluent. Compound 13 was obtained as
yellow crystals in 89% yield; mp 190–1928C; IR (KBr): n=
741 (s), 814 (w), 903 (m), 968 (s), 1041 (s), 1238 (s), 1292 (s),
1443 (m), 1585 (s), 1659 (vs), 2341 (w), 3252 (s), 3298 (m)
1-Methyl-4-phenyl-1H-1,2,3-triazole (18): Recrystalliza-
tion from EtOH/H2O (3:1) gave compound 18 as colorless
crystals in 86% yield; mp 1258C; IR (KBr): n=698 (s), 768
(s), 976 (w), 1076 (m), 1192 (m), 1219 (m), 1454 (m), 1724
1
(w), 2932 (m), 3124 (m) cmÀ1; H NMR (CDCl3, 250 MHz):
d=4.15 (s, 3H), 7.30–7.46 (m, 3H), 7.40 (s,1H), 7.82 (dd,
2H, J1 =7.1, J2 =1.0 Hz); 13C NMR (CDCl3, 62.9 MHz): d=
36.7, 120.6, 125.7, 128.1, 128.8, 130.5; MS: m/z (%)=160
(M+ +1, 4.1), 159 (M+, 22.5), 130 (44.5), 116 (100), 89 (46.0),
63 (25.0); anal. calcd. for C9H9N3 (159.188): C 67.90, H 5.70;
found: C 67.79, H 5.57.
1
cmÀ1; H NMR (CDCl3, 250 MHz): d=2.55 (s, 2H), 4.93 (s,
4H), 7.49 (dd, 2H, J1 =8.4, J2 =1.1 Hz), 7.66 (t, 2H, J=
8.2 Hz), 7.91 (dd, 2H, J1 =7.7, J2 =1.1 Hz); 13C NMR
(CDCl3, 62.9 MHz): d=57.2, 77.9, 80.5, 120.3, 120.9, 124.9,
133.7, 134.8, 157.1, 183.6; MS: m/z (%)=314 (M+À2, 8.4),
313 (1.5), 236 (9.6), 173 (6.3), 149 (10.5), 129 (15.9), 111
(19.2), 83 (51.5), 57 (100); anal. calcd. for C20H12O4
(316.307): C 75.94, H 3.82; found: C 76.12, H 4.01.
1-Allyl-4-phenyl-1H-1,2,3-triazole (19): Purification by
plate chromatography, eluting with n-hexane/ethyl acetate
(10/1), gave compound 19 in 83% yield; IR (neat): n=698
(s), 764 (s), 933 (w), 991 (w), 1045 (w), 1076 (w), 1443 (m),
1,8-Bis[(1-benzyl-1H-1,2,3-triazol-4-yl)methoxy]anthra-
9,10-quinone (14): Recrystallization from EtOH/H2O (3:1)
gave compound 14 as a yellow powder in 72% yield; mp
195–1968C; IR (KBr): n=744 (s), 980 (s), 1049 (s), 1242 (s),
1281 (s), 1315 (s), 1458 (m), 1585 (s), 1670 (vs), 3445 (m)
1608 (w), 1720 (m), 2928 (m), 3074 (w) cmÀ1 1H NMR
;
(CDCl3, 250 MHz): d=4.96 (d, 2H, J=6.1 Hz), 5.29 (dd,
2H, J1 =16.9, J2 =10.2 Hz), 5.86–6.08 (m, 1H), 7.23–7.42 (m,
3H), 7.69 (s, 1H), 7.76 (dd, 2H, J1 =8.5, J2 =1.1 Hz);
13C NMR (CDCl3, 62.9 MHz): d=52.8, 118.7, 119.4, 120.2,
125.7, 128.2, 128.8, 129.0, 129.5, 131.3; anal. calcd. for
C11H11N3 (185.225): C 71.33, H 5.99; found: C 71.19, H 5.79.
4-Phenyl-1-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]-1H-
1,2,3-triazole (20): Recrystallization from EtOH/H2O (3:1)
gave compound 20 as colorless crystals in 71% yield; mp
2438C; IR (KBr): n=521 (w), 690 (s), 760 (s), 914 (w), 984
(m), 1041 (m), 1080 (s), 1188 (s), 1230 (m), 1427 (m), 1458
1
cmÀ1; H NMR (CDCl3, 250 MHz): d=5.31 (s, 4H), 5.43 (s,
4H), 7.13–7.25 (m, 10H), 7.39 (dd, 2H, J1 =8.3, J2 =0.9 Hz),
7.53 (t, 2H, J=7.6 Hz), 7.71 (s, 2H), 7.78 (dd, 2H, J1 =7.6,
J2 =0.9 Hz); 13C NMR (CDCl3, 62.9 MHz): d=54.1, 64.0,
120.1, 121.1, 123.4, 124.9, 128.4, 128.7, 129.0, 133.9, 134.6,
134.7, 144.2, 157.7, 182.4, 183.5; MS: m/z (%)=584 (M+ +2,
1.4), 583 (M+ +1, 4.9), 582 (M+, 5.3), 411 (3.5), 250 (3.0),
240 (12.0), 144 (27.4), 91 (100); anal. calcd. for C34H26N6O4
(582.608): C 70.09, H 4.50; found: C 70.21, H 4.66.
(m), 3016 (w), 3082 (s) cmÀ1
;
1H NMR (DMSO-d6,
250 MHz): d=7.12 (s, 2H), 7.30–7.51 (m, 6H), 7.84 (d, 2H,
J=7.2 Hz); 13C NMR (DMSO-d6, 62.9 MHz): d=35.1, 37.5,
47.4, 51.6, 52.3, 66.7, 77.6, 80.9, 112.3, 122.0, 146.0, 167.2;
MS: m/z (%)=304 (M+ +2, 0.9), 303 (M+ +1, 4.6), 302 (M+,
7.0), 262 (9.1), 245 (9.6), 231 (0.9), 194 (4.5), 171 (8.2), 129
(94.0), 103 (41.5), 83 (47.5), 69 (62.6), 55 (100); anal. calcd.
for C17H14N6 (302.333): C 67.54, H 4.67; found: C 67.66, H
4.78.
1-Benzyl-4-butyl-1H-1,2,3-triazole (15): Purification by
plate chromatography, eluting with n-hexane/ethyl acetate
(10/2), gave compound 15 in 76% yield; IR (neat): n=698
(s), 737 (s), 1018 (s), 1207 (m), 1454 (s), 1497 (m), 2338 (w),
2816 (m), 2874 (m), 3028 (s) cmÀ1
;
1H NMR (CDCl3,
250 MHz): d=0.81 (t, 3H, J=7.0 Hz), 1.17–1.56 (m, 4H),
2.35–2.62 (m, 2H), 5.38 (s, 2H), 7.03–7.26 (m, 5H), 7.38 (s,
1H); 13C NMR (CDCl3, 62.9 MHz): d=13.8, 22.7, 25.3, 31.5,
53.9, 120.5, 126.8, 127.9, 128.9, 134.6, 149.1; anal. calcd. for
C13H17N3 (215.294): C 72.52, H 7.96; found: C 72.37, H 7.79.
(1-Benzyl-1H-1,2,3-triazol-4-yl)methanol (16):Recrystal-
lization from EtOH/H2O (3:1) gave compound 16 as color-
less crystals in 81% yield; mp 78–78.58C; IR (KBr): n=690
(s), 721 (s), 769 (m), 841 (s), 1014 (s), 1038 (s), 1130 (m),
4-Phenyl-1-(2-{2-[2-(4-phenyl-1H-1,2,3-triazol-1-yl)eth-
AHCTUNGERTGoNNUN xy]phenoxy}ethyl)-1H-1,2,3-triazole (22): Recrystallization
from EtOH gave compound 22 as colorless crystals in 69%
yield; mp 107–1088C; IR (KBr): n=690 (s), 744 (s), 764 (s),
1049 (s), 1126 (s), 1219 (s), 1257 (s), 1450 (m), 1508 (s), 1593
1
(m), 2098 (w), 2874 (w), 3128 (m), 3445 (m) cmÀ1; H NMR
216
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Adv. Synth. Catal. 2009, 351, 207 – 218

Copper Nanoparticles on Charcoal for Multicomponent Catalytic Synthesis
FULL PAPERS
(CDCl3, 250 MHz): d=4.27 (t, 4H, J=5.1 Hz), 4.64 (t, 4H,
J=5.1 Hz), 6.74–6.88 (m, 4H), 7.19–7.36 (m, 6H), 7.71–7.76
(m, 4H), 7.89 (s, 2H); 13C NMR (CDCl3, 62.9 MHz): d=
49.9, 67.9, 115.5, 121.1, 122.8, 125.6; MS: m/z (%)=424
(M+ÀN2, 5.0), 423 (3.3), 245 (15.0), 144 (39.2), 121 (100.0),
91 (91.7), 83 (94.2), 57 (65.8); anal. calcd. for C26H24N6O2
(452.508): C 69.01, H 5.35; found: C 68.87, H 5.51.
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4-Phenyl-1-(2-phenylethyl)-1H-1,2,3-triazole (23): Recrys-
tallization from EtOH/H2O (3:1) gave compound 23 as col-
orless crystals in 85% yield; mp 1398C; IR (KBr): n=694
(s), 734 (m), 764 (s), 845 (w), 976 (w), 1084 (m), 1223 (m),
1
1454 (m), 3086 (s) cmÀ1; H NMR (CDCl3, 250 MHz): d=
3.25 (t, 2H, J=7.2 Hz), 4.63 (t, 8H, J=7.2 Hz), 7.14 (d, 2,
J=7.6 Hz), 7.25–7.44 (m, 6H), 7.47 (s, 1H), 7.77 (d, 2H, J=
7.1 Hz), 7.66 (t, 2H, J=8.1 Hz), 7.89 (d, 2H, J=7.6 Hz);
13C NMR (CDCl3, 62.9 MHz): d=36.7, 51.7, 120.1, 125.7,
127.1, 128.1, 128.8, 130.8, 137.1, 147.4; MS: m/z (%)=251
(M+ +2, 1.4), 250 (M+ +1, 6.1), 249 (M+, 14.6), 220 (12.1),
193 (7.9), 179 (4.7), 130 (26.4), 118 (53.0), 105 (100), 77
(51.3), 51 (25.6); anal. calcd. for C16H15N3 (249.311): C 77.08,
H 6.06; found: C 76.93, H 5.91.
Acknowledgements
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We gratefully acknowledge the support of this work by the
Shiraz University Research Council. We are also grateful to
Mr. H. Sajedian Fard and Mr. M. S. Darvish Tafvizi for help-
ful cooperation.
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