Synthesis, characterization and application of Ni0.5Zn0.5Fe2O4 nanoparticles for the one pot synthesis of triaryl-1: H -imidazoles

Article abstract of DOI:10.1039/c6ra05158h

In this investigation, Ni_0.5Zn_0.5Fe₂O₄, as an efficient and heterogeneous catalyst, was prepared and characterized by IR, EDX, XRD and SEM analyses. Ni_0.5Zn_0.5Fe₂O₄ was successfully used for the synthesis of 2,4,5-triaryl substituted imidazoles by the one-pot, three component reaction under solvent-free conditions. Efficiency, generality, high yield, cleaner reaction profiles, ease of product isolation, short reaction times and simplicity are some advantages of this study.

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Synthesis, characterization and application of Ni0.5Zn0.5Fe2O4
nanoparticles for the one pot synthesis of triaryl-1H-imidazoles
Ardeshir Khazaei*a, Heidar Ali Alavi Nik*a, Azam Ranjbarana, Ahmad Reza Moosavi-Zareb
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
In this investigation, Ni0.5Zn0.5Fe2O4, as an efficient and heterogeneous catalyst, was prepared and characterized by IR, EDX, XRD and
SEM analyses. Ni0.5Zn0.5Fe2O4 was successfully used for the synthesis of 2,4,5ꢀtriaryl substituted imidazoles by the oneꢀpot three
component reaction under solventꢀfree condition. Efficiency, generality, high yield, cleaner reaction profiles, ease of product isolation,
short reaction time and simplicity are some advantages of this work.
10
In 1858 the synthesis of imidazole as an important compound was
first reported by Debus.1 The biological roles of imidazoles such
Ni0.5Zn0.5Fe2O4 as Feꢀbased metallic nanoparticles and catalysts
with high yield, short reaction time, cleaner reaction profiles and
as antithrombotic agents, antiꢀinflammatory,2 fungicidal,3 55 ease of product isolation.
therapeutic agents4 act in inhibitors for example P38 MAP
R1
R1
H
O
15 kinase,5 BꢀRaf Kinase,6 calcium antagonist and inhibitors of
thromboxane A2 Synthesase,7 antitumor agents,8 antiꢀHIV9 and
HMG CoA reductase (HMGR).10 Imidazoles have used in the
synthesis and application of a large class of compounds such as
ionic liquids and imidazole related Nꢀheterocyclic carbenes.11ꢀ13
20 2,4,5ꢀTriarylimidazoles were first synthesized from 1,2ꢀ
dicarbonyl compounds, aldehydes and ammonia by Redziszewski
and Japp in 1882.14 Several procedures have been reported for the
synthesis of triarylꢀ1Hꢀimidazoles by the condensation reaction of
αꢀhydroxyketones with ammonium acetate and various aromatic
25 aldehydes in the presence of ionic liquids,15 HOAc,16 H2SO4,17
DMSO,18 H3PO4,19 silica sulfuric acid,20 sulfanilic acid,21
NiCl2.6H2O,22 iodine,23 CAN,24 NaHSO3,25 zeolites HY/silica
gel,26 ZrCl4,27 tetrabutyl ammonium bromide,28 InCl3.H2O,29
Ni0.5Zn0.5Fe2O4 (5 mol%)
Solvent free, 80 oC
O
N
+
2 NH4OAc
+
O
N
H
R2
R1
R2
R1
Scheme 1. The Synthesis of 2,4,5ꢀtriaryl imidazoles.
Results and discussion
At first, According to previous literature,32b,c Ni0.5Zn0.5Fe2O4
60 nanoparticles as mixed metal oxides, have been prepared and
characterized using FTꢀIR and XRD, EDX and SEM analyses.
IR spectrum of Ni0.5Zn0.5Fe2O4 nanoparticles was recorded and
shown in Figure 1. As it is shown in figure 1, indicates that the
prepared ferrite, with spinel structure, has two principle metal–
65 oxygen bands which are appeared at about 572 cm−1 related to
stretching vibrations of metal at the tetrahedral site (FeꢀO). In
other hands, the octahedral–metal stretching vibrations, related to
NiꢀO and ZnꢀO), are appeared at about 419 cm−1.36
30
KMnO4/CuSO4 and microwave irradiation in presence Al2O3 or
30 HOAc.31 Some of these synthetic methods suffer from one or
more drawbacks such as harsh reaction conditions, poor yield,
laborious workꢀup and purifications, prolonged reaction times,
and the use of expensive equipments (microwave or ultrasonic),
corrosive reagents, difficult workꢀup and often extensive acid
35 catalysts. Recently the use of reusable heterogeneous catalysts
and solid acid catalysts have received considerable importance in
organic synthesis because of their several advantages including
operationally simplicity, low toxicity, low cost, and ease of
isolation after completion of the reaction. The synthesis of
40 magnetic nanoparticles as catalysts was gained considerable
interest in recent years due to magnetic properties of these
particles which leads to easy recovery and recycling of the
catalyst.32
70 Fig. 1. FTꢀIR spectrum of Ni0.5Zn0.5Fe2O4 nanoparticles.
33
34
Feꢀbased metallic nanoparticles such as CoFe2O4 , ZnFe2O4
,
35
45 Fe3O4 with general ferrite formula (MFe2O4), were considered
as very good magnetic properties, which M is one of the transition
elements besides of Fe including Zn, Mn, Ni, Co and etc. Ni–Zn
ferrites are the most versatile magnetic materials as they have
high saturation magnetization, high curie temperature, chemical
50 stability and relatively high permeability.32
In another study, The X ray diffraction (XRD) pattern of the
catalyst was studied in a domain of 5–90° (Fig 2) (JCPDS No.08ꢀ
0234). As it is shown in Figure 2, indicates that XRD pattern
displayed diffraction lines of a high crystalline nature at 2θ ≈
75 30.00°, 35.50°, 43.00°, 53.50°, 57.10°, 62.5°, and several small
lines in the 15–90° range which is in good agreement with
previous litratures.36
Herein, we have reported a simple and efficient method for the
synthesis of 2,4,5ꢀtriaryl substituted imidazoles using
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techniques. SEM of the catalyst clearly showed that the particles
have not completely agglomerated and prepared in nano size
(Figure 4). As it is shown in Figure 4, indicates that the spherical
15 structure with only one type of particle morphology, has almost
28 to 43 nm in size.
Fig. 2. XRD pattern of Ni0.5Zn0.5Fe2O4 nanoparticles.
To confirm the nanostructure of Ni0.5Zn0.5Fe2O4, TEM
measurements were performed as showed in Figure 3. TEM
micrograph confirms the presence of particles in Nano size.
5
Fig. 4. SEM images for Ni0.5Zn0.5Fe2O4 nanoparticles.
Kinds of elements in Ni0.5Zn0.5Fe2O4 nanoparticles were studied
20 by Energy dispersive Xꢀray (EDX) on the surface of the catalyst.
The results of the EDX analysis of Ni0.5Zn0.5Fe2O4 nano particles
were proved the existence of Zn, Fe, Ni and O elements (Figure
5). The actual chemical composition of the nanoparticles and the
abundance of the elements were specified using the ICPOES
25 (inductively coupled plasma optical emission spectroscopy)
method (YvonꢀJobin, France).
FeKα
3500
3000
O Kα
2500
2000
FeLα
1500
ZnLα
NiLα
1000
NiKα
FeKβ
NaKα
500
ZnKα
NiKβ
ZnKβ
keV
0
0
5
10
Fig. 5. EDX analysis of Ni0.5Zn0.5Fe2O4 nanoparticles.
In the next step, to optimize the reaction conditions, as a model
30 reaction, a mixture of benzil (1 mmol), ammonium acetate (2.2
mmol) benzaldehyde (1 mmol) was stirred in the presence of
different amount of Ni0.5Zn0.5Fe2O4 under different temperatures
and solventꢀfree conditions. The respective results are depicted in
Table 1. As it can be seen in Table 1, 5 mol % of Ni0.5Zn0.5Fe2O4
35 was sufficient to catalyze the reaction at 80 °C under solventꢀfree
conditions.
Figure 3. Transmission electron micrographs (TEM) of
Ni0.5Zn0.5Fe2O4 nanoparticles.
10 Scanning electron microscopy (SEM) and energy dispersive Xꢀ
ray spectroscopy (EDX) are widely used in the surface analytical
2
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Table 1. Effect of different amounts of the catalyst and temperatures on
the reaction of benzil (1 mmol), ammonium acetate (2.2 mmol)
benzaldehyde (1 mmol) under solvent free conditions.
To study the kinds of the catalyst, we examined the model
25 reaction in the presence of other Lewis acids such as Fe3O4, ZnO
and ZnFe2O4 in comparison with Ni0.5Zn0.5Fe2O4 (Table 4). As it
is shown in Table 4, indicates that Ni0.5Zn0.5Fe2O4 is more
successful than these mentioned catalysts on the synthesis of
2,4,5ꢀtriaryl substituted imidazoles.
Entry
Catalyst
Catalyst
(mol%)
Temp Time
Yielda
(%)
TOFb
(°C)
80
80
80
80
25
60
70
80
(min)
(minꢀ1)
1
2
3
4
5
6
7
8
Ni0.5Zn0.5Fe2O4
Ni0.5Zn0.5Fe2O4
Ni0.5Zn0.5Fe2O4
Ni0.5Zn0.5Fe2O4
Ni0.5Zn0.5Fe2O4
Ni0.5Zn0.5Fe2O4
Ni0.5Zn0.5Fe2O4
Ni0.5Zn0.5Fe2O4
3
4
5
6
5
5
5
5
18
77
81
88
88
25
60
70
80
1.42
1.68
1.76
1.46
0.08
0.34
0.60
1.60
12
30 Table 4. Study of kinds of catalyst on the synthesis of 2,4,5ꢀtriarylꢀ1Hꢀ
imidazole.
10
10
Entry
Catalyst
Catalyst
(mol%)
Temp
(°C)
Time
(min)
Yielda
(%)
TOFb
(minꢀ1)
0.38
60
1
2
3
Fe3O4
ZnO
5
5
5
85
95
80
45
18
16
87
88
87
35
0.97
1.08
23
ZnFe2O4
10
aIsolated yield, bTurn over frequency.
aIsolated yield, bTurn over frequency.
Ease of recycling of the catalyst is one of the most advantages of
this work. For this purpose, the reaction of benzil, ammonium
35 acetate and benzaldehyde was tested by reused catalyst. We have
not observed significant loss of the yields when Ni0.5Zn0.5Fe2O4
was reused for four runs. The results were depicted in Table 5.
5
We also tasted this obtained reaction condition (5 mol % of
Ni0.5Zn0.5Fe2O4) using different solvents. The results are depicted
in Table 2. As it is shown at Table 2, indicates that solventꢀfree
conditions is better than solvent conditions for the synthesis of
2,4,5ꢀtriaryl substituted imidazoles.
Table 5. The Results of the preparation of 2,4,5ꢀTriphenylꢀ1Hꢀimidazole
in the presence of Recycled Ni0.5Zn0.5Fe2O4.
10 Table 2 Effects of solvent on the reaction of benzil (1 mmol), ammonium
acetate (2.2 mmol) benzaldehyde (1 mmol) in the presence of
Ni0.5Zn0.5Fe2O4 (5 mol%).
Yielda (%)
Entry
Solvent
Conditions
Time (min)
Yielda (%)
Entry
Cycle
Time (min)
1
2
3
4
5
ꢀ
10
10
10
10
10
88
86
83
80
78
1
2
3
4
5
6
ꢀ
80 °C
10
36
88
58
88
ꢀꢀꢀ
20
10
1
2
3
4
Acetonitrile
Ethanol
Reflux
Reflux
Reflux
Reflux
Reflux
25
Water
90
Dichloromethane
Toluene
100
100
40 aIsolated yield.
aIsolated yield.
Also, the results of this work have been compared with the
previous reported methods in Table 6. As it is shown in Table 6
indicates that our work is more superior to some previous work.
Catalytic activity of Ni0.5Zn0.5Fe2O4 was improved by the increase
45 of catalytic surface of the catalyst in nano size.
In another step, catalytic activity of Ni0.5Zn0.5Fe2O4 nanoparticles
15 as an efficient and heterogeneous catalyst was investigated in the
synthesis of 2,4,5ꢀtriarylꢀ1Hꢀimidazoles by the oneꢀpot, three
component condensation reaction of ammonium acetate, aromatic
aldehydes with various benzil compounds (Scheme 1 and Table
Table 6. Comparison the results of this work with previous reported
catalysts.
3).
20 Table 3 Synthesis of 2,4,5ꢀtriarylꢀ1Hꢀimidazoles using various benzil,
ammonium acetate, aromatic aldehydes in the presence of Ni0.5Zn0.5Fe2O4
(5% mole) under solvent free conditions.
Entry
Catalyst
Conditions
Time (min) Yielda (%) [Ref]
Entry
R1
H
H
H
H
H
H
H
R2
Time (min)
Yielda (%)
1
2
3
KH2PO4, (5 mol%)
Yb(OPf)3
Ethanol, reflux
C10F18, 80 °C
40
360
45
93 [37]
80 [38]
87 [39]
1
2
3
4
5
6
7
H
10
14
12
16
25
15
15
88
89
91
86
79
90
87
2ꢀCl
[EMIM]OAc
EtOH, ultrasonic
irradiation, r.t.
4ꢀCl
4
6
InCl3.H2O
CH3OH, r.t.
492
10
76 [40]
88c
4ꢀMe
4ꢀOMe
4ꢀBr
2ꢀOMe
Ni0.5Zn0.5Fe2O4,
(5 mol%)
Solvent free, 80 °C
aIsolated yield, cOur work.
42
In a purposed mechanism which are supported by the literature,41,
50 ammonia which is exposed from NH4OAc, attacks to carbonyl group of
the activated aldehyde and produces 1,2ꢀdiamine (I). In the next step, by
the reaction of 1,2ꢀdiamine with activated benzyl and the elimination of
two molecule of H2O, II is prepared. [1,5] hydrogen shift of II, prepared
2,4,5ꢀtriaryl imidazoles.
2,4ꢀ
dichloro
8
H
18
90
9
H
4ꢀNO2
H
30
16
35
87
76
65
10
11
4ꢀMe
4ꢀMe
4ꢀMeO
aIsolated yield.
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45
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IIIFe
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II
NH4OAc
NH3
NH3
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NH2
O
O
Ni(Zn)
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R
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- H2O
H2N
R
NH3
H
N
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I
III
Fe
O
O
IIIFe
O
II
Ni(Zn)
O
Ph
Ph
Ph
Ph
Ph
Ph
O
H2N
H2N
H
R
N
N
N
II
R
R
N
H
O
- 2 H2O
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In this work, 2,4,5ꢀtriarylꢀ1Hꢀimidazole have been synthesized in
the presence of a catalytic amount of Ni0.5Zn0.5Fe2O4, as a
recyclable and heterogeneous catalyst. Ni0.5Zn0.5Fe2O4
nanoparticles were synthesized and characterized by IR, EDX,
10 XRD and SEM analyses. Green reaction conditions, good yields,
easy workꢀup, short reaction times and efficiency of the catalyst
are some advantages of this work.41, 42
Acknowledgements
We gratefully acknowledge the support of this work by
15 Research Council of BuꢀAli Sina University.
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aFaculty of Chemistry, BuꢀAli Sina University, Hamedan 6541835583
Iran. Fax: +98ꢀ81ꢀ38380709; Tel: +98ꢀ81ꢀ38282807; Email: Eꢀmail:
Khazaei_1326@yahoo.com, ali_31006@yahoo.com
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DOI: 10.1039/C6RA05158H
36 N. M. Deraza and O. H. AbdꢀElkaderb, J. Anal. Appl. Pyrpol., 2014,
106, 171ꢀ176; K. H. Wu, Y. M. Shin, C. C. Yang, W. D. Ho, J. S. Hsu,
Journal of Polymer Science: Part A: Polymer Chemistry, 2006, 44, 2657–
2664.
159.9 ppm; IR (KBr, cmꢀ1): 3419, 3029, 1598, 1497, 1449, 1130, 1067,
970, 823, 765, 729, 693, 671.
2ꢀ(4ꢀMethoxyphenyl)ꢀ4,5ꢀdiphenylꢀ1Hꢀimidazole: (5) M.p.: 232ꢀ235 °C;
1H NMR (400 MHz, DMSOꢀd6): δ = 3.82 (s, 3H), 7.06 (d, 2H, J = 6.8 Hz),
5
37 R. S. Joshi, P. G. Mandhane, M. U. Shaikh, R. P. Kale, C. H. Gill, 75 7.23ꢀ7.58 (m, 10H), 8.05 (d, 2H, J = 7.2 Hz), 12.56 (br, 1H) ppm; 13C
Chin. Chem. Lett., 2010, 21, 429–432.
NMR (100 MHz, DMSOꢀd6): δ = 55.7, 114.6, 123.5, 126.9, 127.2, 127.5,
128.0, 128.1, 128.6, 128.8, 129.1, 131.6, 131.7, 135.8, 137.2, 146.0,
146.1, 159.9 ppm; IR (KBr, cmꢀ1): 3431, 3060, 1614, 1493, 1293, 1249,
38 M. Shen, C. Cai, W. Yi, J. Fluorine Chem., 2008, 129, 541ꢀ544.
39 H. Zang, Q. Su, Y. Mo, B.W. Cheng, S. Jun, Ultrason. Sonochem.,
2010, 17, 749ꢀ751.
1177, 1030, 968, 829, 765, 695.
1
10 40 S. D. Sharma, P. Hazarika, D. Konwar, Tetrahedron Lett., 2008, 49, 80 2ꢀ(4ꢀBromophenyl)ꢀ4,5ꢀdiphenylꢀ1Hꢀimidazole: (6) M.p.: 264ꢀ266 °C; H
2216ꢀ2220.
NMR (400 MHz, DMSOꢀd6): δ = 7.25 (t, 1H, J = 7.4 Hz), 7.33 (t, 2H, J =
7.0 Hz), 7.40 (t, 1H, J = 7.8 Hz), 7.46 (t, 2H, J = 7.2 Hz), 7.51ꢀ7.58 (m,
6H), 8.12 (d, 2H, J = 7.2 Hz), 12.82 (br, 1H) ppm; 13C NMR (100 MHz,
DMSOꢀd6): δ = 127.12, 127.44, 127.59, 128.42, 128.71, 128.91, 129.59,
41 M. A. Zolfigol, V. Khakyzadeh, A. R. MoosaviꢀZare, A. Zare, P.
ArghavaniꢀHadi, Z. Mohammadi and M.H. Beyzavi, S. Afr. J. Chem.,
2012, 65, 280–285.
15 42 K. F. Shelke, S. B. Sapkal, S. S. Sonar, B. R. Madje, B. B. Shingate, 85 129.63, 129.59, 131.33, 133.31, 135.42, 137.78, 144.79 ppm; IR (KBr,
and M. S. Shingare, Bull. Korean Chem. Soc. 2009, 30, 1057ꢀ1060.
Synthesis of nano Ni0.5 Zn0.5Fe2O4: In order to obtain the desired
compositions, stoichiometric amounts of NiCl2.6H2O, ZnCl2 and
FeCl3.6H2O were dissolved in ultraꢀpure water. The solutions of
cmꢀ1): 3447, 3030, 1598, 1499, 1482, 1450, 1431, 1131, 1071, 825, 765,
730, 693, 501.
2ꢀ(2ꢀMethoxyphenyl)ꢀ4,5ꢀdiphenylꢀ1Hꢀimidazole: (7) M.p.: 208ꢀ210 °C;
1H NMR (400 MHz, DMSOꢀd6): δ = 3.93 (s, 3H), 7.08 (t, 1H, J = 7.2 Hz),
20 NiCl2.6H2O, ZnCl2 and FeCl3 6H2 O in their stoichiometry (100 ml of 0.05 90 7.17ꢀ7.24 (m, 2H), 7.30 (t, 2H, J = 7.2 Hz ), 7.38ꢀ7.50 (m, 6H), 7.54 (d,
M NiCl2.6H2O, 100 ml of 0.2 M FeCl3.6H2O, 100 ml of 0.05 M ZnCl2)
were dissolved in distilled water with constant stirring. The
neutralization was carried out with 1.5 M sodium hydroxide solution. The
reaction temperature was kept at 85°C for 45 min. The pH of the reaction
2H, J = 7.2 Hz ), 8.06 (d, 1H, J = 7.6 Hz), 11.93 (br, 1H) ppm; 13C NMR
(100 MHz, DMSOꢀd6): δ = 56.02, 112.12, 119.3, 121.07, 126.9, 127.55,
127.7, 128.11, 128.03, 129.06, 129.1, 129.32, 130.28 131.64, 135.7,
136.87, 143.99, 156.47 ppm; IR (KBr, cmꢀ1): 3448, 3063, 1603, 1587,
a
25 was kept at 12. The precipitates were thoroughly washed with distilled 95 1478, 1469, 1445, 1249, 1101, 1020, 764, 747, 694, 613.
water until the washings were free from sodium and chloride ions. The
product was dried in an electric oven at a temperature of 120°C for
overnight to remove water contents. The dried powder was mixed
homogeneously in a cleaned agate mortar and pestle42
2ꢀ(2,4ꢀDichlorophenyl)ꢀ4,5ꢀdiphenylꢀ1Hꢀimidazole: (8) M.p.: 178ꢀ180 °C;
1H NMR (400 MHz, DMSOꢀd6): δ = 7.26ꢀ7.59 (m, 11H), 7.79 (d, 1H, J =
7.6 Hz), 7.86 (d, 1H, J = 7.6 Hz), 12.76 (br, 1H) ppm; 13C NMR (100
MHz, DMSOꢀd6): δ = 127.15, 127.68, 127.95, 128.34, 128.73, 129.17,
100 129.31, 130.22, 131.2, 132.92, 133.06, 134.37, 135.39, 142.76 ppm; IR
(KBr, cmꢀ1): 3446, 3070, 1595, 1550, 1503, 1476, 1426, 1323, 1135, 1099,
881, 770, 698, 498.
30 42 General procedure for the synthesis of 2,4,5ꢀtriarylꢀ1Hꢀimidazoles:
To a mixture of benzil (1mmol), ammonium acetate (2.2 mmol) and
aromatic aldehyde (1 mmol) in a test tube Ni0.5Zn0.5Fe2O4 nanoparticles
(0.0118 g, 5mol%) was added and the resulting mixture was stirred in an
oilꢀbath at 80°C for the appropriate time. After completion of the reaction,
2ꢀ(4ꢀNitrophenyl)ꢀ4,5ꢀdiphenylꢀ1Hꢀimidazole: (9) M.p.: 240ꢀ242 °C; 1H
NMR (400 MHz, DMSOꢀd6): δ = 7.27ꢀ7.75 (m, 10H), 7.90ꢀ8.37 (m, 4H),
35 as monitored by TLC, ethanol was added and the mixture stirred for 5 105 13.17 (br, 1H), ppm; 13C NMR (100 MHz, DMSOꢀd6): δ = 124.74, 126.21,
min. The magnetic Ni0.5Zn0.5Fe2O4 nanoparticles were separated from the
products using an external magnet and then washed twice with acetone,
dried in a desiccator and stored for another subsequent reaction runs (the
catalyst reused seven times in subsequent reaction without any significant
127.68, 128.96, 136.51, 143.76, 146.99 ppm; IR (KBr, cmꢀ1): 3392, 3078,
1598, 1579, 1513, 1442, 1336, 1246, 1111, 970, 853, 763, 6954.
2ꢀPhenylꢀ4,5ꢀdiꢀpꢀtolylꢀ1Hꢀimidazole: (10) M.p.: 269ꢀ271°C; 1H NMR
(400 MHz, DMSOꢀd6): δ = 2.30 (s, 3H), 2.36 (s, 3H), 7.12 (d, 2H, J = 8.0
40 changes in the yield and reaction times). The mixture was poured in cold 110 Hz), 7.25 (d, 2H, J = 8.0 Hz), 7.38ꢀ7.50 (m, 7H), 8.09 (d, 2H, J = 7.6 Hz),
water (50 ml), the precipitated solid was filtered, washed several times
with water, dried and recrystallized from EtOH or acetone:water (9:1) to
get the corresponding 2,4,5ꢀtriarylꢀ1Hꢀimidazoles. The pure products
(compounds 1 – 11) were identified by IR, 1H, 13CNMR and mass spectra.
12.61 (br, 1H) ppm; 13C NMR (100 MHz, DMSOꢀd6): δ = 21.25, 21.33,
125.6, 127.49, 128.22, 128.62, 128.7, 129.14, 129.24, 129.67, 130.84,
132.88, 136.02, 137.37, 137.50, 145.53 ppm; IR (KBr, cmꢀ1): 3436, 3029,
1519, 1500, 1478, 1412, 1322, 1124, 816, 719, 690.
45 43 2,4,5ꢀTriphenylꢀ1Hꢀimidazole: (1) M.p.: 275ꢀ276 °C; 1H NMR (400 115 2ꢀ(4ꢀmethoxyphenyl)ꢀ4,5ꢀdipꢀtolylꢀ1Hꢀimidazole: (11) M.p.: 258ꢀ260 °C;
MHz, DMSOꢀd6): δ = 7.24 (t, 1H, J = 7.2 Hz), 7.32 (t, 2H, J = 7.2 Hz),
7.39 (t, 2H), 7.44ꢀ7.53 (m, 6H), 7.57 (d, 2H, J = 7.6 Hz), 8.10 (d, 2H, J =
7.2 Hz), 12.76 (1H, br) ppm; 13C NMR (100 MHz, DMSOꢀd6): δ = 125.66,
127.03, 127.55, 128.28, 128.66, 128.76, 128.9, 128.95, 129.18, 129.2,
1H NMR (400 MHz, DMSOꢀd6): δ = 2.36 (s, 6H), 3.82 (s, 3H), 7.11ꢀ7.13
(d, 2H, J = 8.0 Hz), 7.23ꢀ7.30 (dd, 4H, J = 8.0 Hz), 7.38ꢀ7.40 (d, 2H, J =
8.0 Hz), 7.44ꢀ7.45 (d, 2H, J = 7.8 Hz), 8.06ꢀ8.08 (d, 2H, J = 8.0 Hz),
12.54 (br, 1H) ppm; 13C NMR (100 MHz, DMSOꢀd6): δ = 21.33, 55.77,
50 130.74, 131.47, 135.6, 137.57, 145.85 ppm; IR (KBr, cmꢀ1): 3433, 3029, 120 124.40, 127.48, 127.89, 128.29, 128.44, 129.10, 129.22, 129.65, 129.72,
1598, 1499, 1453, 1199, 1128, 964, 766, 734, 696.
133.10, 136.02, 137.57, 137.79, 138.13, 148.73 ppm; IR (KBr, cmꢀ1):
3441, 3018, 1523, 1498, 1429, 1321, 1126, 970, 820, 728.
1
2ꢀ(2ꢀChlorophenyl)ꢀ4,5ꢀdiphenylꢀ1Hꢀimidazole: (2) M.p.: 198ꢀ200 °C; H
NMR (400 MHz, DMSOꢀd6): δ = 7.24 (t, 1H, J = 7.1 Hz), 7.31ꢀ7.39 (m,
3H), 7.42ꢀ7.53 (m, 6H), 7.57 (d, 2H, J = 7.2 Hz) 7.61ꢀ7.64 (m, 1H), 7.81ꢀ
55 7.83 (m, 1H), 12.69 (br, 1H) ppm; 13C NMR (100 MHz, DMSOꢀd6): δ =
127.08, 127.7, 128.24, 128.39, 128.7, 129.18, 130.46, 130.68, 130.73,
131.31, 132.02, 132.07, 135.5, 137.37, 143.8 ppm; IR (KBr, cmꢀ1): 3446,
3061, 1599, 1501, 1478, 1321, 1203, 1068, 762, 692, 604.
1
2ꢀ(4ꢀChlorophenyl)ꢀ4,5ꢀdiphenylꢀ1Hꢀimidazole: (3) M.p.: 262ꢀ264 °C; H
60 NMR (400 MHz, DMSOꢀd6): δ = 7.22ꢀ7.57 (m, 12H), 8.11 (d, 2H, J = 8.4
Hz), 12.81 (br, 1H) ppm; 13C NMR (100 MHz, DMSOꢀd6): δ = 127.12,
127.41, 127.59, 128.42, 128.71, 128.89, 129.27, 129.31, 129.47, 131.33
133.31, 135.42, 137.78, 144798 ppm; IR (KBr, cmꢀ1): 3439, 3060, 1599,
1498, 1485, 1451, 1325, 1130, 1090, 971, 829, 765, 731, 696, 601.
65 2ꢀpꢀtolylꢀ4,5ꢀdiphenylꢀ1Hꢀimidazole: (4) M.p.: 236ꢀ237 °C; 1H NMR (400
MHz, DMSOꢀd6): δ = 2.36 (s, 3H), 7.23 (t, 1H, J = 7.4 Hz), 7.31 (t, 4H, J
= 7.2 Hz), 7.38 (t, 1H, J = 7.2 Hz),7.45 (t, 2H, J = 7.4 Hz), 7.51 (d, 2H, J
= 7.2 Hz), 7.56 (d, 2H, J = 7.6 Hz), 7.99 (d, 2H, J = 8.0 Hz) 12.63 (br, 1H)
ppm; 13C NMR (100 MHz, DMSOꢀd6): δ = 55.67, 114.57, 123.53, 126.92,
70 127.55, 128.1, 128.82, 129.12, 131.63, 135.77, 137.24, 145.19, 146.13,
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DOI: 10.1039/C6RA05158H
Graphical Abstract
Synthesis, characterization and application of Ni0.5Zn0.5Fe2O4
nanoparticles for the one pot synthesis of triaryl-1H-imidazoles
Ardeshir Khazaei*, Heidar Ali Alavi Nik*, Azam Ranjbaran, Ahmad Reza Moosavi-Zare
R1
R1
H
O
O
O
Ni0.5Zn0.5Fe2O4 (5 mol%)
Solvent free, 80 oC
N
+
2 NH4OAc
+
N
H
R2
R2
R1
R1
Ni0.5Zn0.5Fe2O4 nanopowder, as a highly efficient and heterogeneous catalyst, was employed for
the synthesis of 2,4,5-triaryl substituted imidazoles.