MCM-41-SO3H as a highly efficient sulfonic acid nanoreactor for the rapid and green synthesis of some novel highly substituted imidazoles under solvent-free condition

Article abstract of DOI:10.1002/cjoc.201280008

Nanosized MCM-41-SO₃H based on ordered mesoporous silica material with a covalent sulfonic acid group was synthesized and used as acid catalyst for the new, simple, convenient and green synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetra-substituted imidazoles. Also some of synthesis products are new. Echo-friendly protocol, short reaction times, easy and quick isolation of the products and excellent yields are the main advantages of this procedure.

Full text of DOI:10.1002/cjoc.201280008

FULL PAPER
DOI: 10.1002/cjoc.201280008
MCM-41-SO3H as a Highly Efficient Sulfonic Acid Nanoreactor
for the Rapid and Green Synthesis of Some Novel Highly
Substituted Imidazoles under Solvent-Free Condition
Mahdavinia, Gholam Hossein*,a
Amani, Ali Mohammadb
Sepehrian, Hamidc
a Department of Chemistry, Marvdasht Branch, Islamic Azad University, Marvdasht, Iran
b Department of Chemistry, KN Toosi University of Technology, P.O. Box 15875-4416, Tehran, Iran
c Jaber Ibn Hayan Research Laboratories, AEOI, P.O. Box 11365/8486, Tehran, Iran
Nanosized MCM-41-SO3H based on ordered mesoporous silica material with a covalent sulfonic acid group
was synthesized and used as acid catalyst for the new, simple, convenient and green synthesis of 2,4,5-trisubstituted
and 1,2,4,5-tetra-substituted imidazoles. Also some of synthesis products are new. Echo-friendly protocol, short re-
action times, easy and quick isolation of the products and excellent yields are the main advantages of this procedure.
Keywords MCM-41-SO3H, nanocatalyst, highly substituted imidazoles, solvent-free condition, heterogeneous
catalysis, nitrogen heterocycles
Introduction
identified as potential inhibitors of p38 MAP kinase.[11]
Moreover, the synthesis of substituted imidazoles has
drawn attention due to these five-membered ring het-
erocycles, which are present in a wide range of naturally
occurring molecules.[12] In the last decade numerous
methods have been developed for the synthesis of
highly substituted imidazoles by using various catalytic
systems including SiO2/NaHSO4,[13] I2,[14] heteropolya-
cid,[15] HClO4-SiO2,[16] FeCl3-6H2O,[17] L-proline,[18]
BF3•SiO2,[19] WD/SiO2,[20] SBSSA[21] and DABCO.[22]
Also several methods comprise the use of micro-
In recent years more attractive possibilities have
been emerged by the development of various new silica
materials with ordered structure.[1] One of the best-
known examples is MCM-41, which is a structurally
well-ordered mesoporous material with a narrow pore
size distribution between 1.5 and 10 nm, depending on
the surfactant cation and a very high surface area up to
1500 m2•g−1.[2] It has been proved that Si-MCM-41
lacks Brönsted acid sites and exhibits only weak hydro-
gen-bonded type sites.[3,4] An additional possibility to
develop acidic solids is the modification of the surface
of suitable support materials, as the chemical function-
alities of these materials can be uniformly modified by
covalent anchoring of different organic moieties.[5]
While several types of solid sulfonic acids have been
created in recent years, there have been only a few re-
ports about their applications as catalyst in chemical
transformations. Furthermore, to the best of our knowl-
edge, there is no report on the use of these materials as
nanocatalysts in the synthesis of substituted imidazoles.
The obtained nanocatalysts were tested for the synthesis
of some new substituted imidazoles under solvent-free
condition.
wave[23,24]
and
refluxing
in
SiO2-H2SO4,[25]
CH3COOH,[26] ZrCl4,[27] NiCl2-6H2O/Al2O3,[28] CAN,[29]
InCl3-3H2O,[30] ionic liquids[31] and ionic liquids in ul-
trasound irradiation.[32] However, in spite of their poten-
tial utility, many of these methods suffer from draw-
backs such as relatively low to moderate yield, use of
toxic organic solvents, high temperatures and expensive
instruments such as microwave and also corrosive re-
agents. Therefore, the search continues for a better cata-
lyst for the synthesis of substituted imidazoles in terms
of operational simplicity, economic viability and envi-
ronmental care.
Results and Discussion
Interest in imidazole-containing structures arises
from their widespread occurrence in molecules that ex-
hibit significant biological activity such as fungicides,
herbicides,[6] plant growth regulators,[7] anti-inflamma-
tory,[8] anti-allergic[9] and analgesic agents.[10] In par-
ticular, 4,5-diaryl substituted imidazoles have been
The MCM-41 was synthesised according to the pre-
viously described method using cetyltrimethylammo-
nium bromide (C16H33(CH3)3N＋Br－), as the templating
agent.[33] The surfactant template was then removed
from the synthesized material by calcination at 540 ℃
*
E-mail: hmahdavinia@gmail.com
Received April 2, 2011; accepted October 24, 2011.
Chin. J. Chem. 2012, 30, 703—708
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Mahdavinia, Amani & Sepehrian
FULL PAPER
for 6 h. Then MCM-41 reacts with chlorosulfonic acid
to give a white powder which was named “MCM-41-
SO3H”. It is interesting to note that the reaction is easy
and clean without any work-up procedure, because HCl
gas is evolved from the reaction vessel immediately
(Scheme 1).
Scheme 2 MCM-41-SO3H catalyzed synthesis of tri and tetra-
substituted imidazoles
Ph
Ph
O
O
NH4OAc
+
ArCHO
+
2
3
1
Ph
N
Scheme 1 Schematic representation for the preparation of
Ar
Ar
MCM-41-SO3H
MCM-41-SO3H, Neat
100 oC, 9 — 15 min
N
H
4
Ph
Ph
Ph
MCM-41-SO3H, Neat
N
RNH2 , 100 oC, 15 — 35 min
N
5
R
6
nium acetate (1.2 mmol) and benzil (1 mmol) catalyzed
by MCM-41-SO3H was investigated in different sol-
vents under solvent-free condition, in which the results
are shown in Table 1.
MCM-41-SO3H nanoreactor was characterized by
thermogravimetric analysis (TGA), scanning electron
microscopy (SEM), X-ray diffraction (XRD), and
acid-base titrations.[34]
In continuation of our work on the development of
useful synthetic methodologies toward synthesis of het-
erocyclic compounds, the catalytic activity of the Brøn-
sted acid nanoreactor MCM-41-SO3H was tested for the
synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetra-substi-
tuted imidazoles under solvent-free condition (Scheme
2).
We attempted to find technically simple, high-
yielding, solvent-free condition for the synthesis of
these compounds. Therefore, we tried to use MCM-41-
SO3H as catalyst in the cyclocondensation of benzil,
aldehyde, ammonium acetate and aniline. First of all,
the reaction of 4-chlorobenzaldehyde (1 mmol), ammo-
Initial screening studies confirmed that solvent-free
technique is the optimal condition for this reaction. An-
other important point which could be elicited evidently
from these results is that raising the reaction tempera-
ture from 60 to 100 ℃ increased the yield and also
improved the reaction rates (Table 1, Entries 1—11).
Moreover, it is worth mentioning that application of
solvents such as H2O, EtOH and CH3OH did not lead to
better results. Under these conditions, longer reaction
times and very low yields can be observed clearly (Ta-
ble 1, Entries 12—14). Furthermore, one of the most
interesting points in this work is due to very large spe-
cific surface areas, highly ordered pore systems and
moreover, the surface properties (inside the channels) of
the modified sulfonic acid nanoreactor (MCM-41-SO3H)
which shows high activity.
Table 1 Synthesis of 4e using different catalysts and reaction conditions
Entry
1
Catalyst (g)
Solvent
Temperature/℃
Time/min
390
270
210
120
70
Yield/%
—
No catalyst
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Solvent free
Methanol
60
60
2
MCM-41-SO3H (0.01)
MCM-41-SO3H (0.04)
MCM-41-SO3H (0.04)
MCM-41-SO3H (0.005)
MCM-41-SO3H (0.01)
MCM-41-SO3H (0.03)
MCM-41-SO3H (0.04)
MCM-41-SO3H (0.01)
MCM-41-SO3H (0.04)
MCM-41-SO3H (0.1)
MCM-41-SO3H (0.04)
MCM-41-SO3H (0.04)
MCM-41-SO3H (0.04)
20
3
60
20
4
80
40
5
90
65
6
90
50
70
7
90
45
70
8
90
35
70
9
100
100
100
Reflux
Reflux
Reflux
30
78
10
11
12
13
14
10
92
10
92
240
270
240
30
Water
trace
40
Ethanol
704
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Chin. J. Chem. 2012, 30, 703—708

MCM-41-SO3H as a Highly Efficient Sulfonic Acid Nanoreactor for the Rapid and Green Synthesis
After optimization of the reaction condition for the
synthesis of 2,4,5-triarylimidazoles 4a—4h (Scheme 2,
Table 2), the scope and generality of the catalytic role of
MCM-41-SO3H was examined by selecting a four
component synthesis of 1,2,4,5-tetraarylimidazoles 6a
—6l. As expected, excellent yields of product were ob-
tained under solvent-free condition with 0.04 g of
MCM-41-SO3H (Scheme 2, Table 3).
The scope and generality of the above process is il-
lustrated with respect to the reactions of different aro-
matic primary amines and a wide range of aromatic al-
dehydes. Most importantly, it can be observed from Ta-
bles 2 and 3 that aromatic aldehydes carrying either
electron-donating or electron-withdrawing groups did
not show much difference and reacted very well, giving
excellent yields.
tion, the MCM-41-SO3H could be recovered as speci-
fied in the experimental section, the results of which are
given in Table 4. These results showed a good recover-
ability and reusability of MCM-41-SO3H for the syn-
thesis of product 4e. It can clearly be seen that even af-
ter four runs, the recovery percentage is high (Table 4).
The plausible mechanism for the synthesis of sub-
stituted imidazoles in the presence of MCM-41-SO3H
involves the initial formation of diamine intermediate
(A). Intermediate (A), in the presence of MCM-41-
SO3H, cyclocondenses with benzil to form imida-
zol-5-ol intermediate (C), which in turn changes to sub-
stituted imidazoles by elimination of water (Scheme 3).
Conclusions
In conclusion, in comparison to the available syn-
thetic methods for the synthesis of substituted imida-
zoles, we have developed a simple and highly efficient
practical method for the one-pot synthesis of the title
compounds using the MCM-41-SO3H. The yields of
products are very good and the use of toxic solvents is
avoided. Using of MCM-41-SO3H for synthesis of
We then continued our study to examine the reus-
ability and recoverability of the catalyst as an additional
important factor in the field of heterogonous nanocata-
lysts. To achieve this, the model reaction of 4-chloro-
benzaldehyde (1 mmol), ammonium acetate (1.2 mmol)
and benzil (1 mmol) was carried out in the presence of
MCM-41-SO3H (40 mg). After completion of the reac-
Table 2 Preparation of trisubstituted imidazoles catalyzed by MCM-41-SO3H under solvent free condition (Scheme 2)
m.p./℃
Entry
Ar
Product
Time/min
Yield/%
Found
Reported
1
2
3
4
5
6
7
8
9
4-PhCH2O-C6H4
4-MeCONH-C6H4
3-Indol
4a
4b
4c
4d
4e
4f
15
9
92
70
95
92
92
85
95
90
90
232—233
289—290
290—291
276—277
264—265
196—197
236—237
196—197
240—242
—
—
12
10
10
15
10
14
12
—
C6H5
274—275[35]
261—263[35]
196[27]
232—235[36]
196[27]
4-Cl-C6H4
4-NO2-C6H4
4-CN-C6H4
3-NO2-C6H4
4-CHO-C6H4
4g
4h
4i
232—235[14]
Table 3 Preparation of tetrasubstituted imidazoles catalyzed by MCM-41-SO3H under solvent free condition (Scheme 2)
M.p./℃
Entry
Ar
R
Product
Time/min
Yield/%
Found
Reported
1
2
4-CN-C6H4
4-PhCH2O-C6H4
3-Indol
Ph
Ph
6a
6b
6c
6d
6e
6f
30
30
20
25
20
25
25
25
15
20
25
25
87
88
98
91
90
85
85
98
89
92
85
85
197—198
235—236
247—249
224—225
152—154
250—252
180—182
172—174
279—281
162—165
165—167
160—161
—
—
3
Ph
—
221[14]
4
C6H5
Ph
5
4-Cl-C6H4
4-NO2-C6H4
4-Me-C6H4
4-MeO-C6H4
4-HO-C6H4
4-Cl-C6H4
4-Me-C6H4
4-MeO-C6H4
Ph
149—151[14]
244—246[14]
185—188[19]
184—185[14]
280—281[14]
162—165[19]
165—166[19]
157—160[16]
6
Ph
7
Ph
6g
6h
6i
8
Ph
9
Ph
10
11
12
PhCH2
PhCH2
PhCH2
6j
6k
6l
Chin. J. Chem. 2012, 30, 703—708
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Mahdavinia, Amani & Sepehrian
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Scheme 3 Plausible mechanism for the formation of substituted imidazoles
O
O
-
S
O
MCM-41
-H2O
S
O
MCM-41
H
H
R
+
N
Ph
O
O
O
S
H
O
NH2
NHR
O
NH3
O
+
Ph
O
O
+
R NH2
Ar
Ar
H
Ar
H
A
Ph
O
Ph
Ph
HO
HN
N
N
Ph
Ph
N
H
Ar
-H2O
-H2O
Ph
HO
Ar
N
R
R
Ar
NHR
C
B
General procedure for the synthesis of tetrasubsti-
Table 4 The recycling of MCM-41-SO3H in synthesis of 4e
tuted imidazoles 6a—6l
Entry
Time/min
Yield/%
92
A mixture of benzil (1 mmol), aldehyde (1 mmol),
ammonium acetate (1.2 mmol), aromatic amine (1
mmol) and MCM-41-SO3H (0.04 g), was heated at 100
℃ with stirring for 15—30 min. After completion of
the reaction, same work-up procedure was followed in
the synthesis of 2,4,5-triarylimidazoles (Scheme 2).
1
2
3
4
10
10
10
10
92
85
83
Spectral data of unknown compounds
highly substituted imidazoles and also synthesis of some
novel substituted imidazoles under mild conditions is
the most important aspect of this study. Simple work-up
and a high degree of MCM-41-SO3H reusability are the
other interesting points of the developed procedure. We
expect to find more applications for this catalytic system
in organic synthesis.
2-(4-(Benzyloxyphenyl)-4,5-diphenyl-1H-imidazole
(Table 2, 4a) 1H NMR (300 MHz, DMSO-d6) δ: 5.15
(s, CH2, 2H), 7.13 (d, J＝8.7 Hz, 2H), 7.20—7.58 (m,
15H), 8.04 (d, J＝8.7 Hz, 2H), 12.54 (1H, NH); 13C
NMR (75 MHz, DMSO-d6) δ: 69.3, 114.9, 123.4, 126.4,
126.7, 127.1, 127.3, 127.6, 127.7, 127.9, 128.1, 128.3,
128.4, 128.6, 131.2, 135.3, 136.8, 136.9, 145.6, 158.5;
－
1
IR (KBr) νmax: 3404, 3060, 1609, 1600 cm ; MS m/z
(%): 77 (23.5), 91 (79), 152 (8.5), 165 (23), 283 (30),
311 (100), 402 (72) [M＋]. Anal. calcd for C28H22N2O: C
83.56, H 5.51, N 6.96; found C 83.60, H 5.49, N 7.02.
2-(4-Acetamidophenyl)-4,5-diphenyl-1H-imidazole
(Table 2, 4b) 1H NMR (300 MHz, DMSO-d6) δ: 2.06
(s, 3H, CH3), 7.20—7.31 (m, 3H), 7.26—7.31 (m, 2H),
7.36—7.54 (m, 7H), 7.66 (d, J＝8.7 Hz, 2H), 7.99 (d,
J＝8.7 Hz, 2H), 10.00 (1H, NH), 12.54 (1H, NH); 13C
NMR (75 MHz, DMSO-d6) δ: 24.1, 118.9, 125.1, 125.7,
126.4, 127.0, 127.6, 127.8, 128.1, 128.4, 128.6, 131.1,
135.2, 136.9, 139.4, 145.5, 168.3; IR (KBr) νmax: 3627,
Experimental
Synthesis and functionalization of MCM-41-SO3H
MCM-41 was modified using a 100 mL suction flask
equipped with a constant pressure dropping funnel con-
taining chlorosulfonic acid (0.466 g, 0.004 mol) and a
gas inlet tube for conducting HCl gas over an adsorbing
solution. Into it was charged 1.20 g of MCM-41 and
chlorosulfonic acid was then added dropwise over a
period of 30 min at room temperature. HCl gas evolved
from the reaction vessel immediately. After completion
of addition the mixture was shaken for 30 min, and the
white solid (MCM-41-SO3H) was obtained (1.52 g).[34]
－
1
3049, 1668, 1602, 1549 cm ; MS m/z (%): 77 (8.5),
165 (36.5), 311 (45.7), 353 (100) [M＋]. Anal. calcd for
C23H19N3O: C 78.16, H 5.42, N 11.89; found C 78.15, H
5.41, N 11.87.
General experimental procedure for the preparation
of 2,4,5-triarylimidazole 4a—4h
A mixture of benzil (1 mmol), aldehyde (1 mmol)
ammonium acetate (1.2 mmol) and MCM-41-SO3H
(0.04 g), were heated at 100 ℃ with stirring for 9—15
min. After completion of reaction (monitored by TLC)
the mixture was cooled to room temperature and 20 mL
chloroform/methanol (1∶1) was added. The catalyst
was filtered off and the solids were washed with acetone
(10 mL). The combined acetone solution was then con-
centrated in vacuum to afford crude product. The crys-
talline pure product was obtained by further recrystali-
zation from 9∶1 acetone-water solution (Scheme 2).
3-(4,5-Diphenyl-1H-imidazol-2-yl)-1H-indole (Tab-
le 2, 4c) 1H NMR (300 MHz, DMSO-d6) δ: 7.12—
7.23 (m, 3H), 7.53 (d, J＝7.1 Hz, 2H), 7.64 (d, J＝7.1
Hz, 2H), 8.00 (d, J＝7.1 Hz, 1H), 8.49 (dd, J＝7.1, 6.8
Hz, 1H), 11.40 (1H, NH), 12.3 (1H, NH); 13C NMR (75
MHz, DMSO-d6) δ: 106.8, 111.6, 119.7, 121.5, 121.8,
123.8, 125.1, 125.7, 126.1, 126.9, 127.4, 128.2, 128.7,
131.6, 135.8, 136.0, 136.3, 143.7; IR (KBr) νmax: 34.14,
－
1
3056, 1622, 1599 cm ; MS m/z (%): 77 (8.5), 101 (7.0),
128 (10.0), 204 (5.4), 231 (14.7), 335 (100) [M＋]. Anal.
calcd for C23H17N3: C 82.36, H 5.11, N 12.53; found C
706
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Chin. J. Chem. 2012, 30, 703—708

MCM-41-SO3H as a Highly Efficient Sulfonic Acid Nanoreactor for the Rapid and Green Synthesis
82.33, H 5.14, N 12.48.
105.7, 111.1, 119.9, 121.8, 122.1, 123.4, 126.1, 128.3,
128.4, 129.0, 129.1, 129.4, 129.5, 130.8, 131.2, 134.9,
2,4,5-Triphenyl-1H-imidazole (Table 2, 4d) 1H
NMR (300 MHz, DMSO-d6) δ: 7.27—8.10 (m, 15H),
12.69 (1H, NH); 13C NMR (75 MHz, DMSO-d6) δ:
122.5, 127.0, 128.7, 129.2, 136.4.
135.5, 136.2, 137.1, 143.5; IR (KBr) νmax: 3419, 1603,
－
1
1570 cm ; MS m/z (%): 77(35), 165 (71), 206 (15.5),
297 (7.7), 353 (4), 410 (63.5), 411 (100) [M＋]. Anal.
calcd for C29H21N3: C 84.64, H 5.14, N 10.21; found C
84.65, H 5.12, N 10.21.
2-(4-Chlorophenyl)-4,5-diphenyl-1H-imidazole
(Table 2, 4e) 1H NMR (300 MHz, DMSO-d6) δ: 7.21
—8.10 (m, 14H), 12.77 (sbr, 1H, NH); 13C NMR (75
MHz, DMSO-d6) δ: 126.6, 126.8, 127.0, 127.8, 128.2,
128.4, 128.5, 128.6, 128.7, 129.1, 130.1, 132.7, 134.9,
137.2, 144.4.
2-(4-Nitrophenyl)-4,5-diphenyl-1H-imidazole
(Table 2, 4f) 1H NMR (300 MHz, DMSO-d6) δ: 7.40
—7.64 (m, 10H), 7.92 (d, J＝8.0 Hz, 2H), 8.50 (d, J＝
8.0 Hz, 2H), 12.30 (s, 1H, NH); 13C NMR (75 MHz,
DMSO-d6) δ: 118.7, 122.5, 124.2, 125.4, 126.3, 126.8,
127.6, 127.8, 128.4, 129.7, 130.6, 131.5, 142.9, 148.7.
2-(4-Cyanophenyl)-4,5-diphenyl-1H-imidazole
(Table 2, 4g) 1H NMR (300 MHz, DMSO-d6) δ: 7.31
(d, J＝8.2 Hz, 2H), 7.51—7.86 (m, 10H), 7.89 (d, J＝
8.2 Hz, 2H), 11.85 (s, 1H, NH); 13C NMR (75 MHz,
DMSO-d6) δ: 110.3, 116.1, 122.4, 124.2, 124.9, 125.9,
126.4, 127.8, 127.9, 128.2, 129.7, 130.6, 131.5, 142.9,
147.9.
1,2,4,5-Tetraphenyl-1H-imidazole (Table 3, 6d)
1H NMR (300 MHz, DMSO-d6) δ: 7.17—7.39 (m,
20H).
2-(4-Chlorophenyl)-1,4,5-triphenyl-1H-imidazole
(Table 3, 6e) 1H NMR (300 MHz, DMSO-d6) δ: 7.30
—7.60 (m, 15H), 7.69 (d, J＝8.2 Hz, 2H), 7.97 (d, J＝
8.4 Hz, 2H).
2-(4-Nitrophenyl)-1,4,5-triphenyl-1H-imidazole
(Table 3, 6f) 1H NMR (300 MHz, DMSO-d6) δ: 7.60
—7.10 (m, 17H), 8.12 (d, J＝8.7 Hz, 2H); 13C NMR (75
MHz, DMSO-d6) δ: 123.4, 124.0, 124.2, 127.0, 127.9,
128.2, 128.5, 128.6, 128.7, 128.8, 128.9, 129.2, 129.3,
129.4, 129.5, 129.9, 131.0, 131.8, 133.8, 136.5, 136.6,
140.1, 144.2, 147.1.
2-(4-Methylphenyl)-1,4,5-triphenyl-1H-imidazole
(Table 3, 6g) 1H NMR (300 MHz, DMSO-d6) δ: 2.85
(s, 3H, CH3), 7.12 (d, J＝8.2 Hz, 2H), 7.27—7.36 (m,
15H), 7.46 (d, J＝7.5 Hz, 2H); 13C NMR (75 MHz,
DMSO-d6) δ: 21.3, 126.5, 127.4, 127.6, 127.8, 128.1,
128.2, 128.4, 128.8, 128.9, 130.6, 130.7, 131.1, 134.5,
137.2, 138.1, 147.1.
2-(4-Methoxyphenyl)-1,4,5-triphenyl-1H-imidazole
(Table 3, 6h) 1H NMR (300 MHz, DMSO-d6) δ: 3.73
(s, 3H, OCH3), 6.84 (d, J＝8.3 Hz, 2H), 7.21—7.37 (m,
15H), 7.55 (d, J＝7.5 Hz, 2H); 13C NMR (75 MHz,
DMSO-d6) δ: 55.2, 113.9, 123.3, 125.9, 126.2, 126.7,
127.2, 127.9, 128.5, 128.7, 129.0, 129.7, 130.3, 130.9,
131.0, 134.5, 137.6, 147.9, 159.9.
2-(4-Hydroxyphenyl)-1,4,5-triphenyl-1H-imidazole
(Table 3, 6i) 1H NMR (300 MHz, DMSO-d6) δ: 6.84
—7.50 (m, 17H), 7.75 (d, J＝8.4 Hz, 2H), 8.37 (s, 1H);
13C NMR (75 MHz, DMSO-d6) δ: 123.2, 123.9, 124.3,
127.1, 127.3, 127.4, 127.7, 128.1, 128.5, 128.8, 129.1,
129.4, 129.6, 130.1, 131.0, 132.1, 134.0, 136.2, 136.9,
139.2, 144.4, 158.1.
2-(3-Nitrophenyl)-4,5-diphenyl-1H-imidazole
(Table 2, 4h) 1H NMR (300 MHz, DMSO-d6) δ: 7.35
—7.52 (m, 10H), 7.81 (d, J＝8.0 Hz, 1H), 8.23 (d, J＝
7.8 Hz, 1H), 8.53 (d, J＝7.5 Hz, 1H), 8.59 (s, 1H),
13.10 (s, 1H, NH); 13C NMR (75 MHz, DMSO-d6) δ:
119.4, 122.6, 127.1, 128.4, 128.7, 130.4, 131.2, 131.8,
143.4, 148.4.
2-(4-Cyanophenyl)-1,4,5-triphenyl-1H-imidazole
(Table 3, 6a) 1H NMR (300 MHz, DMSO-d6) δ: 7.18
—7.35 (m, 9H), 7.51—7.56 (m, 6H), 7.92 (d, J＝8.0 Hz,
2H), 8.25 (d, J＝8.0 Hz, 2H); 13C NMR (75 MHz,
DMSO-d6) δ: 118.9, 125.5, 126.4, 127.1 128.2, 128.5,
128.6, 128.7, 129.3, 129.6, 131.0, 132,1, 132.7, 134.0,
134.2, 136.2, 143.7; IR (KBr) νmax: 3060, 2225, 1608,
－
1
1490 cm ; MS m/z (%): 77 (35.5), 89 (19.0), 165
(194.1), 190 (15.0), 267 (8.0), 297 (10.0), 321 (27.0),
397 (100) [M＋]. Anal. calcd for C28H19N3: C 84.61, H
4.82, N 10.57; found C 84.59, H 4.87, N 10.51.
2-(4-(Benzyloxy)phenyl)-1,4,5-triphenyl-1H-imid-
azole (Table 3, 6b) 1H NMR (300 MHz, DMSO-d6) δ:
5.15 (s, 2H, CH2), 7.12 (d, J＝8.5 Hz, 2H), 7.11—7.55
(m, 20H), 8.01 (d, J＝8.5 Hz, 2H); 13C NMR (75 MHz,
DMSO-d6) δ: 69.3, 115.0, 123.4, 126.4, 126.7, 127.1,
127.7, 127.8, 128.2, 128.3, 128.5, 128.6, 129.2, 131.2,
135.3, 136.8, 136.9, 145.6, 158.5; IR (KBr) νmax: 3054,
1578 cm ; MS m/z (%): 77 (35), 91 (91), 165 (64), 283
(16), 296(26), 311 (100), 387 (38), 402 (36.5), 478 (13)
[M＋]. Anal. calcd for C34H26N2O: C 85.33, H 5.48, N
5.85; found C 85.26, H 5.53, N 5.86.
3-(1,4,5-Triphenyl-1H-imidazol-2-yl)-1H-indole
(Table 3, 6c) 1H NMR (300 MHz, DMSO-d6) δ: 6.20
(s, 1H), 7.16—7.18 (m, 3H), 7.24—7.28 (m, 7H), 7.38
—7.42 (m, 6H), 7.57—7.60 (d, J＝7.5 Hz, 2H), 8.58 (s,
1H), 11.16 (s, 1H); 13C NMR (75 MHz, DMSO-d6) δ:
1-Benzyl-2-(4-Chlorophenyl)-4,5-diphenyl-1H-imi-
dazole (Table 3, 6j) 1H NMR (300 MHz, DMSO-d6)
δ: 5.11 (s, 2H, CH2), 6.97—7.98 (m, 19H); 13C NMR
(75 MHz, DMSO-d6) δ: 48.1, 125.5, 126.0, 126.5,
127.2, 128.1, 128.4, 128.5, 128.9, 129.5, 130.1, 130.2,
130.4, 130.6, 133.8, 134.9.
1-Benzyl-2-(4-methylphenyl)-4,5-diphenyl-1H-imi-
dazole (Table 3, 6k) 1H NMR (300 MHz, DMSO-d6)
δ: 2.45 (s, 3H, CH3), 5.09 (s, 2H, CH2), 6.80 (d, J＝4.2
Hz, 2H), 7.12—7.33 (m, 13H), 7.57 (d, J＝7.5 Hz, 4H);
13C NMR (75 MHz, DMSO-d6) δ: 21.3, 48.2, 125.9,
126.2, 126.7, 127.2, 128.0, 128.5, 128.7, 128.9, 129.2,
129.8, 131.0, 131.1, 134.5, 137.6, 137.9, 138.8, 148.2.
1-Benzyl-2-(4-methoxylphenyl)-4,5-diphenyl-1H-
－
1
imidazole (Table 3, 6l)
DMSO-d6) δ: 3.81 (s, 3H, OCH3), 5.08 (s, 2H, CH2),
1H NMR (300 MHz,
Chin. J. Chem. 2012, 30, 703—708
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
707

Mahdavinia, Amani & Sepehrian
FULL PAPER
139, 31
6.80—6.92 (m, 4H), 7.12—7.31 (m, 11H), 7.58 (d, J＝
7.8 Hz, 4H); 13C NMR (75 MHz, DMSO-d6) δ: 48.1,
55.2, 113.9, 123.3, 125.9, 126.2, 126.7, 127.2, 127.9,
128.5, 128.7, 129.0, 129.7, 130.3, 130.9, 131.0, 134.5,
137.6, 147.9, 159.9
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708
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Chin. J. Chem. 2012, 30, 703—708